KR20160007760A - Catalysts including carbon-nitrogen-oxygen structure and Method for preparing the same - Google Patents
Catalysts including carbon-nitrogen-oxygen structure and Method for preparing the same Download PDFInfo
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- H01M4/00—Electrodes
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- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
본 발명은 탄소 담지체; 상기 탄소 담지체와 C-O-N 또는 C-N 결합을 통해 결합되고 질소기를 포함하며 heterocyclic 형태의 고분자; 및 상기 고분자와 배위결합으로 결합된 금속을 포함하는 연료전지용 또는 레독스 플로우 전지용 촉매 및 그 제조방법에 관한 것이다.
The present invention relates to a carbon carrier; A heterocyclic polymer which is bonded to the carbon support through CON or CN bonds and contains a nitrogen group; And a catalyst for a fuel cell or a redox flow battery comprising a metal bound to the polymer by coordination bonding, and a process for producing the same.
연료의 산화에 의해서 생기는 화학에너지를 직접 전기에너지로 변환시키는 연료전지는 차세대 에너지원으로 각광 받고 있으며 특히 자동차 관련 분야에서 연비절감, 배출가스 저감, 친환경 이미지 등의 이점 때문에 상용화를 위한 연구가 활발히 진행되고 있다. 특히, 연료전지의 전극에서 발생하는 산화, 환원반응의 촉매에 관한 연구가 많이 진행되고 있다.
Fuel cells, which convert chemical energy generated by oxidation of fuel directly into electric energy, are attracting attention as next generation energy sources. Especially, in the automobile related fields, researches for commercialization are actively carried out because of advantages such as fuel consumption reduction, emission gas reduction, . Particularly, researches on oxidation and reduction reaction catalysts occurring in electrodes of fuel cells have been conducted.
고분자 전해질 연료전지(PEMFC)의 상용화를 위해서는 성능, 가격 그리고 내구성 문제를 해결해야 한다. 이러한 문제는 모두 연료전지의 촉매와 밀접한 관련이 있다. 고분자 전해질 연료전지는 작동온도가 낮기 때문에 느린 산소 환원 반응의 속도를 증가시키기 위해서 백금과 같은 귀금속을 촉매로 사용하고 있다. 그러나, 백금은 매장량이 제한되어 있고, 매우 고가이기 때문에 상용화 단계가 늦춰지고 있다. 연료전지 차량이 상용화되기 위해서는 kW 당 백금 사용량이 0.2g 이하로 감소되어야 한다고 보고되고 있으나, 백금 촉매의 경우 이론적으로 백금 담지량(0.4 mg/cm2 이하)이 줄어듬에 따라 전압손실이 발생하기 때문에 백금 저감에는 한계가 있다. 산소환원반응의 느린 반응 속도 때문에 환원 전극 내에서는 과전위가 발생하며, 이러한 반응 속도를 개선시키기 위해 합금 촉매 연구가 진행되고 있다.
Commercialization of polymer electrolyte fuel cells (PEMFC) must solve performance, price and durability problems. All of these problems are closely related to the catalyst of the fuel cell. Polymer electrolyte fuel cells use a noble metal such as platinum as a catalyst to increase the rate of slow oxygen reduction reaction because of the low operating temperature. However, platinum has limited reserves and is very expensive, so commercialization is being delayed. In order to commercialize a fuel cell vehicle, it is reported that the amount of platinum used per kW should be reduced to 0.2 g or less. However, the platinum catalyst theoretically has a platinum reduction (less than 0.4 mg / cm 2) There is a limit. Due to the slow reaction rate of the oxygen reduction reaction, overvoltage occurs in the reducing electrode. Alloy catalyst research is under way to improve the reaction rate.
연료전지용 합금 촉매는 전이 금속(M=Ti, V, Cr, Fe, Co, Ni 등)을 함유하고 있는 배향된 면심입방 구조의 Pt3 M에 대한 연구가 활발하다. 탄소 담지 Pt3 M의 제조는 상업용 탄소 담지 백금 촉매를 출발 물질로 하여 금속 전구체를 침착시키고 열처리하는 과정이 전형적이다. 일반적으로, 탄소 담지 백금촉매에 전이 금속 전구체를 첨가하고 수소와 같은 기체상의 환원제를 사용하여 700 ~ 1200℃에서 열처리한다. 그러나, 열처리 공정은 촉매의 합금도를 높여 촉매 활성도를 증가 시키지만, 입자 크기가 증가하고 분산도가 떨어지는 문제점을 가지고 있다.
Alloy catalysts for fuel cells are actively studied for Pt3M with oriented face-centered cubic structure containing transition metals (M = Ti, V, Cr, Fe, Co, Ni, etc.). Carbon-supported Pt3M is typically prepared by depositing a metal precursor with a commercially available carbon-supported platinum catalyst as a starting material and heat-treating it. Generally, a transition metal precursor is added to a carbon-supported platinum catalyst and heat treatment is performed at 700 to 1200 ° C using a gaseous reducing agent such as hydrogen. However, the heat treatment process increases the catalytic activity by increasing the degree of the alloy of the catalyst, but has a problem that the particle size increases and the degree of dispersion decreases.
따라서 최근 이런 고온 열처리 공정 없이 합금 촉매를 제조하는 방법에 대한 연구가 진행되고 있다. Hui 연구진은 카르보닐 착물(carbonyl complex) 방법을 사용하였으며(J. Phys. Chem. 108 (2004) 11024-11034), Xiong 연구진은 마이크로 에멀전(micro-emulsion)법을 사용하여(Electrochim. Acta 50 (2005) 2323-2329) 200℃ 이하에서 합금 촉매를 제조하였다. 그러나 일반적인 콜로이드 방법은 합금도 조절이 어렵고 표면에 전이금속의 농도가 높아 연료전지 환경에서 쉽게 녹아 나온다. Watanabe 연구진은 나노 캡슐(nano capsule) 방법을 통해 원하는 조성의 작은 합금 입자를 제조할 수 있었다(Appl. Mater. Interfaces 2 (2010) 888-895). 그러나 캡슐을 형성하는데 사용된 올레산과 올리일아민의 제거가 어려우며 이는 촉매 활성을 저해하는 단점을 가지고 있다. 현재 저온 합금 촉매 제조방법은 해결해야 할 많은 문제점을 가지고 있어 합금 촉매를 제조하기 위해서는 고온 열처리 과정을 동반해야 한다. Therefore, researches on a method for producing an alloy catalyst without such a high temperature heat treatment process are under way. Hui and colleagues used a carbonyl complex method (J. Phys. Chem. 108 (2004) 11024-11034), Xiong and colleagues used a micro-emulsion method (Electrochim. Acta 50 2005) 2323-2329) An alloy catalyst was prepared at 200 ° C or lower. However, conventional colloidal methods are difficult to control alloys and have a high concentration of transition metal on the surface, which easily dissolves in a fuel cell environment. Watanabe and colleagues were able to fabricate small alloy particles of the desired composition through the nano capsule method (Appl. Mater. Interfaces 2 (2010) 888-895). However, it is difficult to remove oleic acid and oleylamine used for forming capsules, which has the disadvantage of inhibiting catalytic activity. At present, low-temperature alloy catalyst manufacturing methods have many problems to be solved, and therefore, a high-temperature heat treatment process is required to produce alloy catalysts.
이러한 문제점은 레독스 플로우 전지에서도 동일하게 발생하고 있다.
This problem also occurs in the redox flow battery.
본 발명은 상기 합금 촉매의 문제점을 해결하기 위한 새로운 합금 촉매의 제조방법 및 그 제조방법에 의해 제조된 촉매를 제공하기 위한 것이다.The present invention is to provide a method for producing a novel alloy catalyst and a catalyst prepared by the method for solving the problems of the alloy catalyst.
본 발명은 The present invention
탄소 담지체를 용매에 분산시켜 용매를 제조하는 단계; Dispersing the carbon carrier in a solvent to prepare a solvent;
상기 용매에 전도성 고분자 모노머를 첨가하여 탄소 담지체 상에 전도성 고분자를 합성하여 전도성 고분자가 코팅된 탄소 담지체를 제조하는 단계;Adding a conductive polymer monomer to the solvent to synthesize a conductive polymer on the carbon carrier to prepare a carbon carrier coated with a conductive polymer;
상기 전도성 고분자가 코팅된 탄소 담지체에 2 개 이상의 금속 전구체를 도입하여 2 개 이상의 성분을 포함하는 금속을 제조하는 단계;를 포함하는 것을 특징으로 하는 연료전지용 또는 레독스 플로우 전지용 촉매의 제조방법 및 그 제조방법으로 제조된 연료전지용 또는 레독스 플로우 전지용 촉매에 관한 것이다.
And introducing two or more metal precursors into the carbon-coated support on which the conductive polymer is coated to produce a metal containing two or more components. The method for manufacturing a catalyst for a fuel cell or a redox flow battery according to claim 1, And a catalyst for a fuel cell or a redox flow battery produced by the production method.
본 발명의 합금 촉매 제조방법에 의하여 제조된 촉매는 2 개 이상의 금속 성분을 포함하고 있음에도 불구하고 촉매 활성도가 증가되어 백금과 유사한 산소 환원 반응 속도를 가지고 있어, 연료전지 및 레독스 플로우 전지의 셀 성능 향상 및 가격을 낮출 수 있는 효과가 있다.
Although the catalyst prepared by the method of preparing the alloy catalyst of the present invention contains two or more metal components, the catalytic activity is increased to have an oxygen reduction reaction rate similar to that of platinum, so that the cell performance of the fuel cell and the redox flow cell Improvement and lowering the price.
도 1은 탄소 담지체에 전도성 고분자가 코팅되는 방법 및 코팅된 구조에 관한 것이다.
도 2는 탄소 담지체에 전도성 고분자가 코팅되었을 때, 전도성 고분자의 코팅 두께에 관한 것이다.
도 3은 탄소 담지체에 전도성 고분자가 코팅되었을 때, 전도성 고분자의 코팅 두께에 따른 활성도를 LSV(Linear Sweep Voltammetry)로 측정한 그림이다.
도 4는 본 발명에 의해 제조된 촉매의 분산도를 나타내는 그림이다.
도 5는 본 발명에 의해 제조된 촉매 및 상용 촉매의 촉매활성도를 비교한 그림이다.
도 6은 본 발명에 의해 제조된 촉매 표면에서 질소 구조에 관한 것이다.1 shows a method of coating a conductive polymer on a carbon carrier and a coated structure.
FIG. 2 relates to a coating thickness of the conductive polymer when the conductive polymer is coated on the carbon carrier.
FIG. 3 is a graph showing the activity of the conductive polymer according to the thickness of the conductive polymer when the conductive polymer is coated on the carbon carrier by using LSV (Linear Sweep Voltammetry).
4 is a graph showing the degree of dispersion of the catalyst prepared according to the present invention.
FIG. 5 is a graph comparing catalytic activities of the catalyst prepared according to the present invention and a commercial catalyst.
Figure 6 relates to the nitrogen structure at the catalyst surface prepared by the present invention.
이하에서는 본 발명은 더욱 자세하게 설명하고자 한다.
Hereinafter, the present invention will be described in more detail.
본 발명에서는 2 가지 이상의 금속 성분을 포함하는 촉매의 활성도를 향상시키기 위한 새로운 제조방법 및 그 제조방법으로 제조된 촉매에 관한 것이다.
The present invention relates to a new process for improving the activity of a catalyst comprising two or more metal components and a catalyst prepared by the process.
본 발명에서는 촉매의 활성을 향상시키기 위하여 탄소 담지체를 사용하고 상기 탄소 담지체에 전도성 고분자를 도입하며, 상기 전도성 고분자가 코팅된 담지체에 2 가지 이상의 금속 성분을 도입하여 순수 백금 촉매와 유사한 촉매 활성도를 가지는 촉매를 제공하는 것을 목표로 한다.
In the present invention, a carbon carrier is used to improve the activity of the catalyst, a conductive polymer is introduced into the carbon carrier, and two or more metal components are introduced into the carrier coated with the conductive polymer, And to provide a catalyst having activity.
더욱 상세하게는 탄소 담지체에 전도성 고분자를 도입할 때, 탄소 담지체와 전도성 고분자의 계면 접착력을 향상시키기 위하여 탄소 담지체가 분산된 용액에 전도성 고분자의 모노머를 도입하여 in-situ 고분자화를 통하여 탄소 담지체와 전도성 고분자의 계면 접착력이 향상되었다. 또한, 상기 계면 접착력이 향상된 전도성 고분자가 코팅된 탄소 담지체에 2 가지 금속 성분의 전구체를 도입하여 촉매를 합성하였고, 전구체 상태에서 촉매 합성으로 인하여 금속 성분과 전도성 고분자의 배위 결합이 잘 형성되어 촉매 활성도가 향상되는 효과가 있다.
More specifically, when a conductive polymer is introduced into a carbon carrier, in order to improve the interfacial adhesion between the carbon carrier and the conductive polymer, a monomer of the conductive polymer is introduced into a solution in which the carbon carrier is dispersed, The interfacial adhesion between the carrier and the conductive polymer was improved. In addition, a catalyst was synthesized by introducing a precursor of two metal components into a carbon carrier coated with a conductive polymer having improved interfacial adhesion, and a catalyst was synthesized in a precursor state, so that a coordination bond between a metal component and a conductive polymer was well formed, The activity is improved.
탄소 담지체로는 탄소 나노튜브를 사용하고, 탄소 나노튜브 0.2 g을 초순수 물로 세척하고, 60℃ 오븐에서 건조한다. 건조된 탄소 나노튜브를 20 ml의 에탄올에 혼합하고, 3시간 동안 초음파를 이용하여 분산시킨다. 용매에 분산된 탄소 나노튜브 용액에 0.05 g 피롤 모노머를 용해시키고, 0.06 M 과산화황산암모늄 50ml을 혼합하여 24시간 동안 고분자화 반응을 진행한다. 반응이 종료되면 물과 에탄올로 세척하고, 60℃ 오븐에서 12 시간동안 건조시킨다. 이를 통해, 전도성 고분자가 코팅된 탄소 나노튜브가 제조되었고, 이의 구조를 도 1에 나타내었다.
Carbon nanotubes were used as the carbon support, and 0.2 g of the carbon nanotubes were washed with ultrapure water and dried in an oven at 60 ° C. The dried carbon nanotubes are mixed with 20 ml of ethanol and dispersed by ultrasonic waves for 3 hours. 0.05 g of pyrrole monomer is dissolved in a carbon nanotube solution dispersed in a solvent, and 50 ml of 0.06 M ammonium persulfate is mixed to conduct a polymerization reaction for 24 hours. When the reaction is complete, wash with water and ethanol and dry in an oven at 60 ° C for 12 hours. As a result, a conductive polymer-coated carbon nanotube was prepared, and its structure is shown in FIG.
상기 전도성 고분자가 코팅된 탄소 나노튜브에 금속 성분을 도입하기 위하여, 수소화 붕소 나트륨 환원을 이용하였다. 0.15g 전도성 고분자가 코팅된 탄소 나노튜브를 180 ml 에탄올에 분산시키고, 0.133 g 백금 전구체인 백금 클로라이드 0.133 g 및 0.094 g 니켈 전구체인 니켈 클로라이드 6수화물을 첨가하였다. 상기 용액에 20 ml 에탄올 및 0.1 g 수소화 붕소 나트륨의 혼합용액을 첨가하여 4 시간동안 격렬히 교반한다. 교반이 종료되면 필터를 통해 침전시킨 후 세척하고, 60℃ 오븐에서 12 시간동안 건조시킨다. 제조된 촉매는 전도성 고분자가 코팅된 탄소 나노튜브에 PtNi 금속이 담지된 촉매 (이하 PtNi/PPy-CNT라 한다)이다. 상기 PtNi/PPy-CNT를 질소 분위기에서 300℃에서 3시간 동안 열처리한다.
Sodium borohydride reduction was used to introduce metal components into the conductive polymer-coated carbon nanotubes. 0.15 g of the conductive polymer-coated carbon nanotube was dispersed in 180 ml of ethanol, and 0.133 g of platinum chloride, 0.133 g of platinum precursor, and 0.094 g of nickel chloride hexahydrate, nickel precursor, were added. To this solution is added a mixed solution of 20 ml of ethanol and 0.1 g of sodium borohydride and stirred vigorously for 4 hours. After agitation, precipitate through the filter, wash, and dry in an oven at 60 ° C for 12 hours. The prepared catalyst is a PtNi metal-loaded catalyst (hereinafter referred to as PtNi / PPy-CNT) on a carbon nanotube coated with a conductive polymer. The PtNi / PPy-CNT is heat-treated at 300 ° C for 3 hours in a nitrogen atmosphere.
상기 실시예 1에서 탄소 나노튜브 용액에 0.05 g 피롤 모노머를 용해시키는 대신에 0.1 g의 피롤 모노머를 용해시키는 것을 제외하고는 실시예 1과 동일하게 실시하였다.
The procedure of Example 1 was repeated, except that 0.1 g of the pyrrole monomer was dissolved instead of 0.05 g of the pyrrole monomer dissolved in the carbon nanotube solution.
상기 실시예 1에서 탄소 나노튜브 용액에 0.05 g 피롤 모노머를 용해시키는 대신에 0.15 g의 피롤 모노머를 용해시키는 것을 제외하고는 실시예 1과 동일하게 실시하였다.
The procedure of Example 1 was repeated except that 0.1 g of the pyrrole monomer was dissolved instead of 0.05 g of the pyrrole monomer dissolved in the carbon nanotube solution.
상기 실시예 1∼3의 피롤 모노머의 함량에 따른 두께를 TEM (transmission electron microscope, 투과전자현미경)으로 측정하여 도 2에 나타내었고, 실시예 1은 도 2(a), 실시예 2는 도 2(b), 실시예 3은 도 2(c)에 나타내었다. 실시예 1의 폴리피롤 고분자의 코팅두께는 1.5 nm, 실시예 2는 5 nm, 실시예 3은 7.5 nm이었다. 피롤 모노머의 함량에 따라 코팅된 폴리피롤 고분자의 두께는 증가하였다.
The thickness according to the content of the pyrrole monomer in Examples 1 to 3 was measured with a transmission electron microscope (TEM). The results are shown in Fig. 2. Example 1 is shown in Fig. 2 (a) (b) and Example 3 is shown in Fig. 2 (c). The coating thickness of the polypyrrole polymer of Example 1 was 1.5 nm, that of Example 2 was 5 nm, and that of Example 3 was 7.5 nm. The thickness of the coated polypyrrole polymer increased with the content of pyrrole monomer.
또한, 금속 성분이 없는 상태에서 코팅 두께에 따른 전기적 특성을 측정하기 위하여 LSV로 측정하여 도 3에 나타내었다. 그 결과 폴리피롤 코팅 두께에 따라 전기적 특성이 현격한 차이를 보였으며, 5 nm의 폴리피롤 코팅 두께가 가장 우수한 성능을 나타내었다. 본 발명에서는 전도성 고분자의 두께를 최적화 하였고, 두께에 따라 전기적 특성 변화가 현격하여 두께의 최적화 또한 전기적 특성 변화에 중요한 사항인 것을 확인할 수 있었다. 또한, 코팅 두께에 따른 전기적 특성이 증가하다가 감소하고 이 범위가 1~7 nm의 매우 좁은 범위이므로, 코팅 두께의 최적 범위가 매우 좁고 이의 전기적 특성변화가 현격하게 변화하므로 이의 최적 구간을 찾는 구성은 이 기술분야의 통상의 기술자가 용이하게 발명할 수 있는 정도의 두께 범위가 아니다.
In addition, in order to measure the electrical characteristics according to the thickness of the coating in the absence of the metal component, it is measured by LSV and is shown in FIG. As a result, the electrical properties were remarkably different according to the polypyrrole coating thickness, and the polypyrrole coating thickness of 5 nm showed the best performance. In the present invention, the thickness of the conductive polymer was optimized, and it was confirmed that the change of the electrical characteristic was remarkable according to the thickness, and that the optimization of the thickness was also important for the change of the electrical characteristics. In addition, since the electrical characteristics according to the coating thickness increase and decrease and this range is a very narrow range of 1 to 7 nm, the optimum range of the coating thickness is very narrow and the electrical characteristic changes significantly. Therefore, But is not within the range of thicknesses that can be readily invented by those skilled in the art.
도 4의 (a)는 금속 성분이 포함된 실시예 2 PtNi/PPy-CNT 촉매의 분산도, (b)는 전도성 고분자가 도입되지 않은 PtNi/CNT 촉매의 분산도, 및 (c)는 상용촉매인 Pt/C 촉매의 분산도를 나타내었다. 이는 TEM으로 측정하였으며, 측정한 결과 분산도가 본 발명의 제안한 실시예 2 촉매의 분산도가 다른 촉매의 분산도에 비해 현격하게 향상된 것을 확인할 수 있었다.
FIG. 4 (a) is a dispersion diagram of the PtNi / PPy-CNT catalyst of Example 2 containing a metal component, (b) is a dispersion diagram of a PtNi / CNT catalyst to which a conductive polymer is not introduced, and Of the Pt / C catalyst. This was measured by TEM. As a result, it was confirmed that the dispersity of the catalyst of Example 2 of the present invention was remarkably improved as compared with that of other catalysts.
도 5에서는 상기 실시예 2 PtNi/PPy-CNT 촉매, PtNi/CNT 촉매 및 Pt/C 촉매의 전기적 활성도를 LSV로 측정하였다. 그 결과 본 발명의 PtNi/PPy-CNT 촉매가 동일한 금속 성분을 포함하는 PtNi/CNT 촉매보다 현격하게 우수한 전기적 활성을 나타내었으며, 상용 촉매인 Pt/C 촉매와 유사한 전기적 활성을 나타내었다. 본 발명에서 제안된 촉매는 단가가 높은 Pt/C와 유사한 전기적 활성을 보이면서도 단가가 낮아, 연료전지 및 레독스 플로우 전지의 상용화에 기여할 수 있을 것으로 사료된다.
In FIG. 5, the electrical activity of PtNi / PPy-CNT catalyst, PtNi / CNT catalyst and Pt / C catalyst of Example 2 was measured by LSV. As a result, the PtNi / PPy-CNT catalyst of the present invention exhibited remarkably superior electrical activity than the PtNi / CNT catalyst containing the same metal component, and exhibited similar electrical activity to the Pt / C catalyst of the commercial catalyst. The catalyst proposed in the present invention exhibits similar electrical activity to Pt / C having a high unit cost and has a low unit cost, thus contributing to commercialization of a fuel cell and a redox flow battery.
도 6에서는 폴리피롤 고분자가 탄소 담지체 상에서 합성 및 금속 전구체가 폴리피롤 고분자가 코팅된 탄소 담지체 상에서 합성됨으로 인해, XPS(X-ray photoelectron spectroscopy)로 측정한 결과 표면에서 질소기의 특성 변화가 생겼다. 도 6의 (a)는 금속 성분이 포함되지 않은 전도성 고분자가 코팅된 CNT의 질소기의 특성, 및 (b)는 금속성분이 포함된 전도성 고분자가 코팅된 CNT의 질소기의 특성을 나타낸다. 상기 금속성분이 포함된 전도성 고분자가 코팅된 CNT, 즉 PtNi/PPy-CNT 촉매 표면에서의 질소기는 피롤릭(pyrrolic) 질소가 50 mol% 이상을 포함 및 피리디닉(pyridinic) 질소의 몰 함량이 탄소 담지체의 질소 몰 함량보다 큰 구성을 특징으로 하고 있다. 이는 PtNi/PPy-CNT 촉매에서는 질소기가 금속 성분과 탄소 담지체와 네트워크가 잘 형성하는데 기여한 것으로 인해 촉매 분산도가 향상될 수 있었고, 이로 인해 촉매 활성의 향상에 기여한 것으로 사료된다. 따라서, 촉매 표면에서의 질소기의 특성이 촉매 활성도에 영향을 크게 미치고, 본 발명에서 제안한 촉매 질소기의 특성을 한정하는 구성은 촉매 활성에 크게 영향을 미치므로 이 기술분야의 통상의 기술자가 용이하게 도출할 수 없는 구성이다. In FIG. 6, a polypyrrole polymer was synthesized on a carbon support and a metal precursor was synthesized on a carbon support coated with a polypyrrole polymer. As a result, X-ray photoelectron spectroscopy (XPS) FIG. 6 (a) shows the characteristics of a nitrogen-containing CNT coated with a conductive polymer not containing a metal component, and FIG. 6 (b) shows the characteristics of a nitrogen-containing CNT coated with a metal-containing conductive polymer. The nitrogen group of the conductive polymer-coated CNT, that is, the PtNi / PPy-CNT catalyst surface containing the metal component includes pyrrolic nitrogen in an amount of 50 mol% or more, and the molar amount of pyridinic nitrogen is in the range of carbon Is larger than the nitrogen molar content of the carrier. This suggests that in the PtNi / PPy-CNT catalyst, the nitrogen group contributes to the formation of the network with the metal component and the carbon carrier, thereby improving the catalyst dispersion and thus contributing to the improvement of the catalytic activity. Therefore, since the characteristic of the nitrogen group on the catalyst surface greatly affects the catalytic activity and the structure of limiting the characteristics of the catalytic nitrogen group proposed in the present invention greatly affects the catalytic activity, It is a configuration that can not be derived.
Claims (21)
상기 촉매는 탄소 담지체; 상기 탄소 담지체를 적어도 부분적으로 코팅하고, 질소기를 포함하며 heterocyclic 형태의 전도성 고분자; 및 상기 전도성 고분자와 결합되고 2가지 이상의 성분을 포함하는 금속;을 포함하고,
상기 탄소 담지체와 상기 전도성 고분자는 C-O-N 또는 C-N 결합으로 연결되어 있고,
상기 전도성 고분자와 상기 금속은 배위결합을 통해 연결된 것을 특징으로 하는 연료전지용 또는 레독스 플로우 전지용 촉매
A catalyst for a fuel cell or a redox flow battery,
The catalyst may be a carbon carrier; At least partly coating the carbon support, and comprising a heterocyclic type conductive polymer containing a nitrogen group; And a metal combined with the conductive polymer and containing at least two components,
The carbon carrier and the conductive polymer are connected by CON or CN bonds,
Wherein the conductive polymer and the metal are connected through a coordination bond. The catalyst for a fuel cell or the redox flow battery
The catalyst for a fuel cell or redox flow battery according to claim 1, wherein the nitrogen group at the surface of the catalyst comprises at least 50 mol% of pyrrolic nitrogen
3. The catalyst for a fuel cell or redox flow battery according to claim 2, wherein the nitrogen group at the surface of the catalyst has a molar amount of pyridinic nitrogen larger than that of the carbon support
The catalyst for a fuel cell or redox flow battery according to claim 1, wherein at least one of carbon black, carbon black, activated carbon, graphite, carbon nanotubes and fullerene is selected as the carbon carrier
The catalyst for a fuel cell or redox flow battery according to claim 4, wherein the carbon carrier is a carbon nanotube
The catalyst for a fuel cell or redox flow battery according to claim 1, wherein the conductive polymer is polymerized on a carbon support
The catalyst for a fuel cell or redox flow battery according to claim 6, wherein the conductive polymer comprises at least one or more selected from pyrrole, pyridine, anilyl, and thiophene.
The catalyst for a fuel cell or redox flow battery according to claim 7, wherein the conductive polymer comprises polypyrrole, polyaniline, polypyridine, and polythiophene polymer
The catalyst for a fuel cell or the redox flow battery according to claim 8, wherein the conductive polymer is a polypyridine
The catalyst for a fuel cell or redox flow battery according to claim 1, wherein the metal comprises at least two metal components selected from platinum, iridium, palladium, cobalt, iron, molybdenum,
The catalyst for a fuel cell or the redox flow battery according to claim 10, wherein the metal is platinum and nickel.
탄소 담지체를 용매에 분산시켜 용매를 제조하는 단계;
상기 용매에 전도성 고분자 모노머를 첨가하여 탄소 담지체 상에 전도성 고분자를 합성하여 전도성 고분자가 코팅된 탄소 담지체를 제조하는 단계;
상기 전도성 고분자가 코팅된 탄소 담지체에 2 개 이상의 금속 전구체를 도입하여 2 개 이상의 성분을 포함하는 금속을 제조하는 단계;를 포함하는 것을 특징으로 하는 연료전지용 또는 레독스 플로우 전지용 촉매의 제조방법
A method for producing a catalyst for a fuel cell or a redox flow battery,
Dispersing the carbon carrier in a solvent to prepare a solvent;
Adding a conductive polymer monomer to the solvent to synthesize a conductive polymer on the carbon carrier to prepare a carbon carrier coated with a conductive polymer;
Preparing a metal containing two or more components by introducing two or more metal precursors into the carbonaceous support coated with the conductive polymer to prepare a catalyst for a fuel cell or a redox flow battery
13. The method according to claim 12, wherein the surface nitrogen group of the catalyst comprises at least 50 mol% of pyrrolic nitrogen.
14. The method for producing a catalyst for a fuel cell or a redox flow battery according to claim 13, wherein the surface nitrogen group has a molar amount of pyridinic nitrogen larger than a molar amount of nitrogen of the carbon support
The method of claim 12, wherein the carbon carrier is at least one selected from carbon black, activated carbon, graphite, carbon nanotubes, and fullerene.
The method for producing a catalyst for a fuel cell or a redox flow cell according to claim 15, wherein the carbon carrier is a carbon nanotube
13. The method according to claim 12, wherein the conductive polymer comprises at least one or more of pyrrole, pyridine, anilyl, and thiophene.
18. The method of claim 17, wherein the conductive polymer comprises polypyrrole, polyaniline, polypyridine, and polythiophene polymer.
19. The method according to claim 18, wherein the conductive polymer is a polypyridine, or a method for producing a catalyst for a fuel cell or a redox flow battery
The method according to claim 12, wherein the metal comprises at least two metal components selected from platinum, iridium, palladium, cobalt, iron, molybdenum, chromium and nickel.
21. The method according to claim 20, wherein the metal is made of platinum and nickel.
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