KR-102961655-B1 - Hydrogen gas sensor and manufacturing method thereof

Abstract

The present invention provides a hydrogen gas sensor comprising a polymer coating layer prepared by including a copolymer containing benzophenone-based acrylic repeating units, wherein the polymer coating layer has a cross-linked network structure, so that the hydrogen gas sensing stability with respect to humidity can be more remarkable and a significantly wide operating temperature can be achieved.

Inventors

• 임보규
• 김예진
• 정서현
• 박종목
• 정유진
• 헤녹

Assignees

• 한국화학연구원

Dates

Publication Date

20260508

Application Date

20221025

Claims (17)

1. A hydrogen gas sensor comprising a substrate; and a hydrogen detection layer, A first electrode and a second electrode spaced apart from each other on the hydrogen detection layer; A metal nanoparticle layer formed in a region separated from the first electrode and the second electrode; and A polymer coating layer comprising a copolymer containing benzophenone-based acrylic repeating units located on the metal nanoparticle layer; and The above polymer coating layer has a cross-linked copolymer network structure, is non-porous, and The above hydrogen gas sensor is a hydrogen gas sensor satisfying the following Equation 1: [Equation 1] (In the above Equation 1, A RH0% is the current measured by a hydrogen gas sensor for hydrogen-nitrogen gas at a hydrogen concentration of 0.1 wt% and a relative humidity of 0%, and A RH60% is the current measured by a hydrogen gas sensor for hydrogen-nitrogen gas at a hydrogen concentration of 0.1 wt% and a relative humidity of 60%.
2. In Article 1, A hydrogen gas sensor in which the copolymer contains 1 to 20 mol% of benzophenone-based acrylic repeating units relative to the total molar amount of repeating units.
3. In Article 1, A hydrogen gas sensor in which the copolymer further comprises one or more repeating units selected from methyl methacrylate, methyl acrylate, ethyl methacrylate, and ethyl acrylate.
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6. In Article 1, A hydrogen gas sensor in which the metal nanoparticle layer is formed by being deposited on a portion of the surface of the hydrogen detection layer.
7. In Paragraph 6, A hydrogen gas sensor in which the polymer coating layer is in contact with a hydrogen detection layer in which a metal nanoparticle layer is not formed.
8. In Article 1, The hydrogen gas sensor is a metal oxide comprising one or more metals selected from tin, gallium, indium, and titanium, and the hydrogen detection layer is a hydrogen gas sensor.
9. In Article 1, The above hydrogen detection layer is a polymer layer formed from a first polymer; and A hydrogen gas sensor comprising a composite layer formed from a second polymer-CNT composite on the above polymer layer.
10. In Article 9, A hydrogen gas sensor in which the second polymer-CNT composite is a CNT wrapped by a second polymer, and the polymer layer and the composite layer are connected through a triazole.
11. In Article 1, A hydrogen gas sensor in which the metal of the metal nanoparticle layer comprises one or more selected from palladium (Pd), platinum (Pt), rhodium (Rd) and nickel (Ni).
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13. In Article 1, The above hydrogen gas sensor is a hydrogen gas sensor with an operating temperature of 1 to 100 ℃.
14. A hydrogen gas detection method characterized by detecting hydrogen gas contained in a mixed gas using a hydrogen gas sensor selected from any one of claims 1 to 3, 6 to 11, and 13.
15. In Article 14, A method for detecting hydrogen gas in which the hydrogen concentration in the above-mentioned mixed gas is 0.1 to 100,000 ppm.
16. Step of forming a hydrogen detection layer on a substrate; A step of forming a first electrode and a second electrode spaced apart from each other on the hydrogen detection layer; A step of forming a metal nanoparticle layer in a region separated from the first electrode and the second electrode; and A method for manufacturing a hydrogen gas sensor comprising the step of forming a polymer coating layer by coating a solution containing a copolymer containing benzophenone-based acrylic repeating units onto the metal nanoparticle layer; The step of forming the polymer coating layer comprises the steps of forming a film by coating a solution containing a copolymer containing benzophenone-based acrylic repeating units, photocuring the film by irradiating it with ultraviolet rays, and drying the photocured film. The above polymer coating layer has a cross-linked copolymer network structure, is non-porous, and A method for manufacturing a hydrogen gas sensor in which the above hydrogen gas sensor satisfies the following Equation 1: [Equation 1] (In the above Equation 1, A RH0% is the current measured by a hydrogen gas sensor for hydrogen-nitrogen gas at a hydrogen concentration of 0.1 wt% and a relative humidity of 0%, and A RH60% is the current measured by a hydrogen gas sensor for hydrogen-nitrogen gas at a hydrogen concentration of 0.1 wt% and a relative humidity of 60%.
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Description

Hydrogen gas sensor and manufacturing method thereof The present invention provides a hydrogen gas sensor having significantly superior stability even at high operating temperatures and in high humidity environments, and a method for manufacturing the same. Hydrogen energy, which is emerging due to the depletion of fossil fuels and environmental pollution issues, has the potential to be utilized in almost every field currently used in the energy system, ranging from basic industrial materials to general fuels, hydrogen cars, hydrogen airplanes, fuel cells, and nuclear fusion energy. However, hydrogen gas has a wide explosive concentration range (4–75%) and low ignition energy, meaning it ignites easily even from minute static electricity; therefore, even a trace amount of leakage can be extremely dangerous. Accordingly, high-performance sensors capable of rapidly and accurately detecting hydrogen gas are required to reduce major accidents and casualties caused by hydrogen leaks. To date, various hydrogen gas sensors have been developed, including sensors using catalytic combustion or heating wires, SiO2 and AlN metal oxide (nitride) semiconductors, and sensors using bulk Pd and Pt with SiC, GaN, etc., and Schottky barrier diodes with a two-electrode structure. However, these sensors are not only large in size and complex in structure but also expensive. Furthermore, since they operate at high temperatures above 300°C, they have limitations such as high power consumption and reduced sensitivity to hydrogen. Accordingly, as disclosed in Korean Registered Patent Publication No. 10-0870126, "Method for Manufacturing a Hydrogen Gas Sensor Using Pd Nanowires," research on hydrogen gas sensor materials and structures capable of optimizing performance as a hydrogen gas sensor is currently underway; however, there is still a need to develop a sensor that operates with high sensitivity to hydrogen gas at room temperature. Meanwhile, Korean Patent Application No. 10-2022-0035654 introduced a coating layer containing a thermoplastic polymer into a hydrogen gas sensor to achieve excellent hydrogen gas selectivity. However, while the hydrogen gas sensor exhibited excellent hydrogen selectivity at room temperature, its selectivity decreased at high temperatures, and both hydrogen selectivity and hydrogen detection performance declined with humidity, resulting in a problem of reduced sensing stability in high-temperature and high-humidity environments. Therefore, there is a need to develop a hydrogen gas sensor that not only achieves high sensitivity to hydrogen gas at room temperature but also enables operation at high temperatures and possesses excellent sensing stability against humidity. Figure 1 shows a schematic diagram of a hydrogen gas sensor manufactured in Example 1. Figure 2 shows the NMR measurement diagram of copolymers containing benzophenone acrylate repeating units prepared in Preparation Examples 1 to 3. Figure 3 shows a graph of the current value measured according to humidity of the hydrogen gas sensor manufactured in Example 1. Figure 4 shows a graph of the current value measured according to humidity of the hydrogen gas sensor manufactured in Example 2. Figure 5 shows a graph of the current value measured according to humidity of the hydrogen gas sensor manufactured in Example 3. Figure 6 shows a graph of the current values measured according to humidity of the hydrogen gas sensor manufactured in Comparative Example 1. Hereinafter, a hydrogen gas sensor according to the present invention and a method for manufacturing the same will be described in detail. Unless otherwise defined, technical and scientific terms used herein have the meanings commonly understood by those skilled in the art to which this invention pertains, and descriptions of known functions and configurations that could unnecessarily obscure the essence of the present invention are omitted in the following description. The singular form used in this specification is intended to include the plural form unless specifically indicated otherwise in the context. Additionally, units used herein without special reference are based on weight, and, for example, units of % or ratio mean weight % or weight ratio, and weight % means the weight percentage of any one component of the total composition that occupies the composition, unless otherwise defined. Additionally, the numerical ranges used in this specification include lower and upper limits and all values within the range, increments logically derived from the form and width of the defined range, all of which are limited values, and all possible combinations of upper and lower limits of numerical ranges defined in different forms. Unless otherwise specifically defined in this specification, values outside the numerical range that may occur due to experimental error or rounding are also included in the defined numerical range. In addition, when it is said in the present invention that a layer i