WO2019132053A1 - Carbon felt having boron group introduced thereto and method for surface treatment of carbon felt - Google Patents
Carbon felt having boron group introduced thereto and method for surface treatment of carbon felt Download PDFInfo
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- WO2019132053A1 WO2019132053A1 PCT/KR2017/015510 KR2017015510W WO2019132053A1 WO 2019132053 A1 WO2019132053 A1 WO 2019132053A1 KR 2017015510 W KR2017015510 W KR 2017015510W WO 2019132053 A1 WO2019132053 A1 WO 2019132053A1
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4209—Inorganic fibres
- D04H1/4242—Carbon fibres
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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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
- H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a carbon felt having a boron group incorporated therein, and more particularly, to a method of treating a carbon felt that can introduce a boron group without affecting the surface.
- the electrodes of the redox flow cell should have good electrical conductivity and mechanical strength and be stable chemically and electrochemically.
- it should be a material that can show high efficiency when applied to a battery, is inexpensive, and has an oxidation / reduction reaction with the active material reversibly
- carbon materials are inexpensive, have high chemical resistance in electrolytes such as acids and bases, and can be said to be the most suitable electrode material for redox flow cells because of their easy surface treatment.
- carbon materials carbon felt is widely used as a redox flow electrode because of its chemical resistance, stability in a wide voltage range, and high strength.
- the surface of the carbon felt which is a carbon material, is hydrophobic, it is very important to remove the surface polymer, introduce an oxygen functional group, and improve the hydrophilicity so that the electrolyte solution and the electrode can easily react.
- the redox flow battery has attracted attention as a next-generation high-capacity power storage battery due to advantages such as simplicity of structure and easy size enlargement.
- advantages such as simplicity of structure and easy size enlargement.
- the carbon felt used as the electrode material of the commercial redox flow secondary battery since the surface area is limited and the affinity with the electrolyte is very poor, the energy efficiency is lowered when applied to the redox flow secondary battery without surface treatment There are disadvantages.
- the present invention also provides a carbon felt surface treatment method which improves the energy efficiency of the redox flow secondary battery as a result of improving the wettability by introducing a boron group into the carbon felt to modify hydrophobicity to a strong hydrophilic property.
- a carbon felt having a boron introduced into its surface.
- the redox flow battery used as an energy storage system is attracting attention due to advantages such as simplicity of structure and easy size enlargement but has a problem that the surface area is limited and the affinity with the electrolyte is inferior.
- the inventors of the present invention have confirmed that the hydrophobic carbon felt can be modified to be hydrophilic when the boron group is introduced into the surface of the carbon felt, so that it is easy to apply the carbon felt to the secondary battery. .
- the carbon felt having a boron group introduced into the surface thereof according to the present invention, is characterized in that it has a network structure.
- the term " network structure " of the present invention is a planar net structure in which specific polygons are connected as one of the structures of organic compounds. Since the network structure has a lot of voids and has excellent conductivity, the carbon felt having a network structure can be easily used as an electrode.
- the carbon felt having a boron introduced into the surface thereof according to the present invention, has a wetting angle of 90 DEG or less.
- wetting angle " is a measure indicating the degree of wetting, which means that the smaller the wetting angle is, the better wettability is. In general, it means that the wetting angle is not wet when the wetting angle is more than 90 °.
- the wetting angle of the carbon felt without surface treatment was 99.66 °
- the wetting angle of the carbon felt surface-treated with the boron was 85.54 °.
- the boron precursor may be at least one selected from the group consisting of NH 4 BF 4 , NaBH 4 , KBH 4 , LiBH 4 , B 2 H 6 , B (CH 3 ) 3 or TEB, and is preferably NH 4 BF 4 .
- the heat treatment is performed at 700 to 1000 ° C.
- the carbon felt having the boron introduced thereinto had a boron group introduced into its surface and no change in its structure as compared with the carbon felt not subjected to the surface treatment.
- the CV experiment of the embodiment of the present invention showed that the carbon felt having the boron introduced thereinto had excellent redox characteristics and had a low overvoltage. These results suggest that the capacity and electrochemical characteristics are improved (Experimental Example 4, see Fig. 4).
- an electrode for a redox flow secondary battery comprising carbon felt.
- a redox flow secondary battery comprising an electrode having a carbon felt surface-modified with the boron.
- boron is introduced as a functional group on the surface of the carbon felt, thereby making the hydrophobic carbon felt hydrophilic.
- a vanadium redox flow secondary battery using a carbon felt having a boron introduced therein exhibits an effect of improving energy efficiency.
- FIG. 1 is a SEM photograph showing a surface of a carbon felt surface treated through an embodiment of the present invention.
- Figure 2 shows the EDS results of a surface of a carbon felt surface through an embodiment of the present invention.
- FIG. 3 is a graph illustrating the results of measurement of the wetting angle of the surface of the carbon felt according to an embodiment of the present invention.
- FIG. 4 is a graph illustrating the CV characteristics of the surface-treated carbon felt electrode according to an embodiment of the present invention.
- FIG. 5 is a view showing a unit cell structure in which a surface-treated carbon felt is inserted into an electrode according to an embodiment of the present invention.
- FIG. 6 is a graph showing a result of observing a change in energy efficiency after introduction of a surface-treated carbon felt into an electrode according to an embodiment of the present invention.
- a 2 M NH 4 BF 4 solution as a boron precursor solution was impregnated with a carbon felt electrode and dried in an oven at 80 ° C for 8 hours.
- a carbon felt electrode without surface treatment was prepared.
- EDS (Energy Dispersive Spectroscopy) analysis was performed on the surface-treated carbon felt electrodes prepared in the above examples, and the results are shown in FIG.
- the positive / negative electrode reactivity is improved when the carbon felt to which the surface treatment method according to the present invention is applied is used than the carbon felt not subjected to the surface treatment. This indicates that the activity of the boron formed on the carbon felt surface to which the surface treatment method according to the present invention is applied is greatly increased with respect to the vanadium ion.
- the carbon felt electrode prepared in the above Examples and Comparative Examples was introduced into the electrode in the structure of the unit cell shown in Fig. 5, graphite was introduced into the bipolar plate, Nafion was introduced into the ion exchange membrane, And the voltage efficiency and the energy efficiency were observed. The results are shown in FIG. 6 and summarized in Table 1.
- the energy efficiency of the electrode of the above embodiment is significantly increased compared to that of the electrode of the comparative example. This indicates that the activity of the vanadium ion is greatly increased due to the boron formed on the carbon felt surface.
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Abstract
The present invention relates to carbon felt having a boron group introduced thereto and a method for surface treatment of carbon felt through the introduction of the boron group. The method has the effects of modifying hydrophobic carbon felt to have strong hydrophilicity. In addition, a vanadium redox flow secondary battery comprising the carbon felt having a boron group introduced thereto of the present invention exhibits the effect of increasing in energy efficiency.
Description
본 발명은 보론(boron)기가 도입된 카본펠트에 관한 것으로서, 더욱 상세하게는 표면에는 영향을 미치지 않으면서 보론기를 도입할 수 있는 카본펠트의 표면처리 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon felt having a boron group incorporated therein, and more particularly, to a method of treating a carbon felt that can introduce a boron group without affecting the surface.
최근 친환경 재생 에너지 생산의 필요성이 증가됨에 따라 이를 안정적으로 활용하기 위해서 대용량 에너지 저장 장치에 대한 개발도 증가하고 있다. 에너지 저장 시스템으로서 레독스 플로우 전지의 전극은 전기 전도도와 기계적 강도가 우수해야 하며, 화학적, 전기화학적으로 안정해야 한다. 또한 전지에 적용하였을 때 높은 효율을 보일 수 있어야하고, 가격이 저렴하며, 활성물질과의 산화/환원 반응이 가역적으로 이루어지는 물질이어야 한다Recently, as the need for the production of environmentally friendly renewable energy has increased, the development of large capacity energy storage devices has been increasing to utilize them stably. As the energy storage system, the electrodes of the redox flow cell should have good electrical conductivity and mechanical strength and be stable chemically and electrochemically. In addition, it should be a material that can show high efficiency when applied to a battery, is inexpensive, and has an oxidation / reduction reaction with the active material reversibly
이러한 기준으로 볼 때 탄소재료는 가격이 저렴하고, 산 및 염기 등의 전해질에서 높은 내화학성을 지니고 있으며, 표면처리가 용이하기 때문에 레독스 플로우 전지의 전극재료로 가장 적합하다고 할 수 있다. 특히 탄소재료 중에서도 카본펠트의 경우 내화학성, 넓은 전압 범위에서의 안정성, 고강도의 특성 때문에 레독스 플로우 전극으로 많이 이용되고 있다.Based on these standards, carbon materials are inexpensive, have high chemical resistance in electrolytes such as acids and bases, and can be said to be the most suitable electrode material for redox flow cells because of their easy surface treatment. Among carbon materials, carbon felt is widely used as a redox flow electrode because of its chemical resistance, stability in a wide voltage range, and high strength.
그러나 탄소재료인 카본펠트는 표면이 소수성을 띠기 때문에 전해질 용액과 전극이 용이하게 반응할수 있도록 표면 고분자 제거와 산소 관능기 도입 및 친수성 향상이 매우 중요하다.However, since the surface of the carbon felt, which is a carbon material, is hydrophobic, it is very important to remove the surface polymer, introduce an oxygen functional group, and improve the hydrophilicity so that the electrolyte solution and the electrode can easily react.
레독스 플로우 전지는 구조의 단순성과 용이한 대형화 등의 장점으로 인해 차세대 대용량 전력저장 전지로서 주목 받고 있다. 그러나, 상용 레독스 플로우 이차전지의 전극 소재로 사용되는 카본펠트의 경우, 표면적이 제한적이고 전해액과의 친화성이 매우 떨어지기 때문에 표면처리 없이 레독스 플로우 이차전지에 적용할 경우, 에너지 효율이 낮아진다는 단점이 존재한다. The redox flow battery has attracted attention as a next-generation high-capacity power storage battery due to advantages such as simplicity of structure and easy size enlargement. However, in the case of the carbon felt used as the electrode material of the commercial redox flow secondary battery, since the surface area is limited and the affinity with the electrolyte is very poor, the energy efficiency is lowered when applied to the redox flow secondary battery without surface treatment There are disadvantages.
이러한 문제를 해결하고자 종래 카본펠트에 표면 관능기를 도입하는 방법이 연구 적용되고 있으나, 대부분이 산소 또는 질소로 표면을 개질하는 방법으로 국한되어 있다.In order to solve this problem, a method of introducing a surface functional group into carbon felt has been studied, but most of them are limited to a method of modifying the surface with oxygen or nitrogen.
또다른 기술로는 금속 또는 산화물 계열의 촉매를 이용하는 방법이 제시되고 있으나 사용되는 금속 소재의 경우 Pt, Ir, Pd와 같은 귀금속을 사용하기 때문에 비용이 비싸다는 단점을 가지고 있다.As another technology, a method using a metal or oxide-based catalyst has been proposed. However, the metal material used has a drawback that it is expensive because it uses a precious metal such as Pt, Ir, Pd.
본 발명은 상기 표면에 보론기가 도입된 카본펠트를 제공하는 것을 목적으로 한다.It is an object of the present invention to provide a carbon felt in which a boron group is introduced on the surface.
또한, 본 발명은, 카본펠트에 보론기를 도입하여 소수성을 강한 친수성으로 개질시켜 젖음성을 개선함으로써 결과적으로 레독스 플로우 이차전지의 에너지 효율을 향상시키는 카본펠트 표면 처리방법을 제공함에 있다. The present invention also provides a carbon felt surface treatment method which improves the energy efficiency of the redox flow secondary battery as a result of improving the wettability by introducing a boron group into the carbon felt to modify hydrophobicity to a strong hydrophilic property.
본 발명의 한 양태에 따르면, 본 발명은 표면에 보론기가 도입된 카본펠트를 제공한다.According to one aspect of the present invention, there is provided a carbon felt having a boron introduced into its surface.
에너지 저장 시스템으로서 이용되는 레독스 플로우 전지는 구조의 단순성과 용이한 대형화와 같은 장점으로 인해 주목받고 있으나, 표면적이 제한적이고 전해액과의 친화성이 떨어진다는 문제점이 있다. The redox flow battery used as an energy storage system is attracting attention due to advantages such as simplicity of structure and easy size enlargement but has a problem that the surface area is limited and the affinity with the electrolyte is inferior.
이에, 본 발명자들은 상기와 같은 문제점을 해결하기 위하여 카본펠트 표면에 보론기를 도입시키는 경우, 소수성의 카본펠트를 친수성으로 개질시킬 수 있어 이차전지에 적용이 용이한 것을 확인하고, 본 발명을 완성하게 되었다.In order to solve the above problems, the inventors of the present invention have confirmed that the hydrophobic carbon felt can be modified to be hydrophilic when the boron group is introduced into the surface of the carbon felt, so that it is easy to apply the carbon felt to the secondary battery. .
본 발명의 표면에 보론기가 도입된 카본펠트에 있어서, 상기 카본펠트는 망상구조인 것을 특징으로 한다.In the carbon felt having a boron group introduced into the surface thereof according to the present invention, the carbon felt is characterized in that it has a network structure.
본 발명의 상기 용어 '망상구조'란 유기 화합물의 구조의 하나로서 특정한 다각형이 이어진 평면 그물 모양의 구조이다. 망상구조는 빈공간이 많아 우수한 전도성을 지니기 때문에 망상구조를 갖는 카본펠트는 전극으로서 용이하게 사용될 수 있다.The term " network structure " of the present invention is a planar net structure in which specific polygons are connected as one of the structures of organic compounds. Since the network structure has a lot of voids and has excellent conductivity, the carbon felt having a network structure can be easily used as an electrode.
본 발명에 따른 표면처리처되지 않은 카본펠트는 표면에 탄소-탄소 이중결합(C=C) 기가 형성된 망상구조의 카본펠트일 수 있다. The carbon felt not subjected to the surface treatment according to the present invention may be a carbon felt having a network structure in which a carbon-carbon double bond (C = C) group is formed on the surface.
또한, 상기 표면처리되지 않은 카본펠트에 본원발명에 따른 보론기가 도입된 카본펠트는 탄소-보론 단일 결합(C-B), 탄소-보론 이중결합(C=B)가 형성된 망상구조의 카본펠트일 수 있다.The carbon felt to which the boron according to the present invention is introduced into the non-surface-treated carbon felt may be a carbon felt having a network structure in which a carbon-boron single bond (CB) and a carbon-boron double bond (C = B) are formed .
본 발명의 표면에 보론기가 도입된 카본펠트에 있어서, 상기 카본펠트는 젖음각이 90° 이하인 것을 특징으로 한다.In the carbon felt having a boron introduced into the surface thereof according to the present invention, the carbon felt has a wetting angle of 90 DEG or less.
본 발명의 상기 용어 '젖음각'이란, 젖음의 정도를 나타내는 척도로서, 젖음각의 값이 작을수록 잘 적셔짐을 의미한다. 일반적으로 당업계에서 젖음각이 90°이상일 경우 젖지 않음을 의미한다.The term " wetting angle " of the present invention is a measure indicating the degree of wetting, which means that the smaller the wetting angle is, the better wettability is. In general, it means that the wetting angle is not wet when the wetting angle is more than 90 °.
본 발명의 일 실험예에 따르면, 표면 처리를 수행하지 않은 카본펠트의 젖음각은 99.66°인데 반해 보론기로 표면처리한 카본펠트의 경우 젖음각이 85.54°인 것을 확인하였다. 이러한 결과는, 보론기로 표면처리한 카본펠트가 소수성에서 친수성으로 개질되어 전해액과의 친화성을 높임으로써 에너지 효율을 더 높일 수 있음을 시사한다(실험예 3 및 도 3 참조).According to an experimental example of the present invention, it was confirmed that the wetting angle of the carbon felt without surface treatment was 99.66 °, while the wetting angle of the carbon felt surface-treated with the boron was 85.54 °. These results suggest that the carbon felt surface-treated with the boron is modified from hydrophobic to hydrophilic to increase the affinity with the electrolytic solution (see Experimental Example 3 and FIG. 3).
본 발명의 다른 한 양태에 따르면, 본 발명은According to another aspect of the present invention,
(a) 보론 전구체 용액에 카본펠트를 담지한 후 건조시키는 단계; 및(a) carrying carbon felt on a boron precursor solution and drying the carbon felt; And
(b) 상기 담지된 카본펠트를 열처리하는 단계를 포함하는 카본펠트 표면처리 방법을 제공한다.(b) heat-treating the supported carbon felt.
종래에 카본펠트에 표면 관능기를 도입하는 방법에 이용되는 관능기로서는 산소 또는 질소만 이용되어 왔다. 또한 금속 또는 산화물 계열의 촉매를 이용하여 표면을 개질시키는 방법이 알려져 있으나, 금속으로서 귀금속을 사용하기 때문에 비용이 비싸다는 단점이 있었다. 이에, 본 발명자들은 보론을 새로운 관능기로서 도입하여 카본펠트의 표면을 개질시키는 방법을 발명하였다.Conventionally, only oxygen or nitrogen has been used as a functional group used in a method of introducing a surface functional group into carbon felt. Further, a method of modifying the surface by using a metal or oxide-based catalyst is known, but it is disadvantageous in that it is expensive because a noble metal is used as the metal. The inventors of the present invention invented a method of modifying the surface of carbon felt by introducing boron as a new functional group.
본 발명의 카본펠트 표면처리 방법에 있어서, 상기 보론 전구체는 상기 보론 전구체는 NH4BF4, NaBH4, KBH4, LiBH4, B2H6, B(CH3)3 또는 TEB로 구성된 군으로부터 선택되는 1종 이상인 것을 특징으로 하며, 바람직하게는 NH4BF4인 것을 특징으로 한다.In the carbon felt surface treatment method of the present invention, the boron precursor may be at least one selected from the group consisting of NH 4 BF 4 , NaBH 4 , KBH 4 , LiBH 4 , B 2 H 6 , B (CH 3 ) 3 or TEB, and is preferably NH 4 BF 4 .
본 발명의 카본펠트 표면처리 방법에 있어서, 상기 열처리하는 단계에서는 700 내지 1000 ℃ 에서 열처리하는 것을 특징으로 한다.In the carbon felt surface treatment method of the present invention, the heat treatment is performed at 700 to 1000 ° C.
본 발명의 일 실험예에 따르면, 보론기가 도입된 카본펠트의 경우 표면처리 되지 않은 카본펠트와 비교하였을 때, 표면에 보론기가 도입됨과 동시에 구조는 변함이 없음을 확인하였다. 이러한 결과는, 카본 펠트 표면에 보론기가 도입되어도 표면 구조에는 영향을 주지 않으면서 보론기에 의해 표면이 개질될 수 있음을 보여준다(실험예 1-2, 도 1-2 참조).According to one experimental example of the present invention, it was confirmed that the carbon felt having the boron introduced thereinto had a boron group introduced into its surface and no change in its structure as compared with the carbon felt not subjected to the surface treatment. These results show that even when a boron group is introduced on the carbon felt surface, the surface can be modified by the boron group without affecting the surface structure (see Examples 1-2 and 1-2).
본 발명의 일 실험예에 따르면, 본 발명의 실시예의 CV 실험을 수행한 결과, 보론기가 도입된 카본펠트의 산화 환원 특성이 우수하며 과전압이 적게 걸리는 것을 확인하였다. 이러한 결과는, 용량(capacity) 및 전기화학적 특성이 향상되었음을 시사한다(실험예 4, 도 4 참조).According to one experimental example of the present invention, the CV experiment of the embodiment of the present invention showed that the carbon felt having the boron introduced thereinto had excellent redox characteristics and had a low overvoltage. These results suggest that the capacity and electrochemical characteristics are improved (Experimental Example 4, see Fig. 4).
또한, 본 발명의 일 실험예에 따르면, 본 발명의 실시예의 전압효율 및 에너지 효율 변화를 관찰한 결과, 보론기가 도입되지 않은 비교예보다 보론기가 도입된 본원발명의 실시예의 전하, 전압 및 에너지가 더 증가한 것을 확인하였다. 이러한 결과는, 본원발명 실시예의 전압효율 및 에너지 효율의 증가는 카본펠트 표면에 형성된 보론기로 인해 바나듐 이온에 대한 활성도가 크게 증가하였음을 시사한다(실험예 5, 표 1 참조)As a result of observing the voltage efficiency and energy efficiency change of the embodiment of the present invention, the charge, voltage and energy of the embodiment of the present invention in which the boron is introduced is higher than that of the comparative example in which the boron is not introduced Respectively. These results suggest that the increase in the voltage efficiency and energy efficiency of the present invention example significantly increased the activity against vanadium ions due to the boron group formed on the carbon felt surface (see Example 5, Table 1)
본 발명의 또 다른 한 양태에 따르면, 카본펠트를 포함하는 레독스 플로우 이차전지용 전극을 제 공한다.According to still another aspect of the present invention, there is provided an electrode for a redox flow secondary battery comprising carbon felt.
본 발명의 또 다른 한 양태에 따르면, 본 발명은 상기 보론기로 표면개질된 카본펠트를 도입한 전극을 포함하는 레독스 플로우 이차전지를 제공한다.According to still another aspect of the present invention, there is provided a redox flow secondary battery comprising an electrode having a carbon felt surface-modified with the boron.
상기와 같은 본 발명에 따르면, 카본펠트 표면에 관능기로 보론을 도입함으로써, 소수성의 카본펠트를 친수성으로 개질시키는 효과가 있다.According to the present invention as described above, boron is introduced as a functional group on the surface of the carbon felt, thereby making the hydrophobic carbon felt hydrophilic.
또한, 본 발명에 의하여 보론기를 도입한 카본 펠트를 사용한 바나듐 레독스 플로우 이차전지느 에너지 효율이 향상되는 효과를 나타낸다.Further, according to the present invention, a vanadium redox flow secondary battery using a carbon felt having a boron introduced therein exhibits an effect of improving energy efficiency.
도 1은 본 발명의 일 실시예를 통하여 표면처리된 카본펠트 표면을 관찰한 SEM 사진이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a SEM photograph showing a surface of a carbon felt surface treated through an embodiment of the present invention. FIG.
도 2는 본 발명의 일 실시예를 통하여 표면처리된 카본펠트 표면의 EDS 결과를 도시한 것이다.Figure 2 shows the EDS results of a surface of a carbon felt surface through an embodiment of the present invention.
도 3은 본 발명의 일 실시예를 통하여 표면처리된 카본펠트 표면의 젖음각을 측정한 결과를 도시한 것이다.FIG. 3 is a graph illustrating the results of measurement of the wetting angle of the surface of the carbon felt according to an embodiment of the present invention.
도 4는 본 발명의 일 실시예를 통하여 표면처리된 카본펠트 전극의 CV특성을 측정한 결과이다. FIG. 4 is a graph illustrating the CV characteristics of the surface-treated carbon felt electrode according to an embodiment of the present invention.
도 5는 본 발명의 일 실시예를 통하여 표면처리된 카본펠트를 전극으로 도입한 단위셀 구성도이다.5 is a view showing a unit cell structure in which a surface-treated carbon felt is inserted into an electrode according to an embodiment of the present invention.
도 6은 본 발명의 일 실시예를 통하여 표면처리된 카본펠트를 전극으로 도입한 후, 에너지 효율 변화를 관찰한 결과를 도시한 것이다.FIG. 6 is a graph showing a result of observing a change in energy efficiency after introduction of a surface-treated carbon felt into an electrode according to an embodiment of the present invention.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지는 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.
실시예: 표면처리된 카본펠트 전극Example: Surface treated carbon felt electrode
보론 전구체 용액으로서 2M NH4BF4 용액에 카본펠트 전극을 함침한 후 80 ℃ 오븐에서 8 시간동안 건조한다. A 2 M NH 4 BF 4 solution as a boron precursor solution was impregnated with a carbon felt electrode and dried in an oven at 80 ° C for 8 hours.
건조 후, 800 ℃, 아르곤 분위기에서 2 시간 동안 열처리를 수행한다.After drying, heat treatment is performed at 800 ° C in an argon atmosphere for 2 hours.
비교예: 표면처리 되지 않은 카본펠트 전극Comparative Example: Non-surface-treated carbon felt electrodes
표면처리 하지 않은 카본펠트 전극을 준비하였다.A carbon felt electrode without surface treatment was prepared.
실험예 1: 카본펠트의 표면구조 확인Experimental Example 1: Confirmation of surface structure of carbon felt
상기 실시예 및 상기 비교예에서 제조된 카본펠트 전극에 대하여 SEM을 통하여 표면을 관찰하였으며, 그 결과를 도 1에 도시하였다.The surface of the carbon felt electrode prepared in the above Examples and Comparative Examples was observed through an SEM. The results are shown in FIG.
도 1을 참조하면, 표면처리를 수행하지 않은 카본펠트(도 1의 (a)), 보론기 도입을 위한 표면처리가 수행된 카본펠트(도 1의 (b)) 전극 표면에서 큰 차이점을 관찰되지 않았다. 이는 본 발명에서의 표면처리 방법이 카본펠트 표면구조에는 영향을 주지 않음을 알 수 있다.1, carbon felt (FIG. 1 (a)) without surface treatment, carbon felt (FIG. 1 (b)) subjected to surface treatment for introduction of boron It was not. This indicates that the surface treatment method of the present invention does not affect the carbon felt surface structure.
실험예 2: 표면 처리된 카본펠트의 EDS 분석Experimental Example 2: EDS analysis of surface-treated carbon felt
상기 실시예에서 제조된 표면처리한 카본펠트 전극에 대하여 EDS(Energy Dispersive Spectroscopy) 분석 결과를 수행하였으며, 그 결과를 도 2에 도시하였다.EDS (Energy Dispersive Spectroscopy) analysis was performed on the surface-treated carbon felt electrodes prepared in the above examples, and the results are shown in FIG.
도 2를 참조하면, 카본펠트 전극 표면에서 많은 양의 보론이 관찰되었으며, 이로부터 표면에 보론기가 도입되었음을 확인할 수 있다. 이는 본 발명에 따른 표면처리법을 이용하여 카본펠트 표면에 보론기가 형성되었음을 알 수 있다.Referring to FIG. 2, a large amount of boron was observed on the surface of the carbon felt electrode, and it was confirmed that boron was introduced on the surface. It can be seen that the boron was formed on the surface of the carbon felt by using the surface treatment method according to the present invention.
실험예 3: 카본펠트의 젖음성 확인Experimental Example 3: Determination of Wettability of Carbon Felt
상기 실시예 및 상기 비교예에서 제조된 카본펠트 전극에 대하여 젖음성 실험을 수행하였으며, 그 결과를 도 3에 도시하였다.The wettability test was performed on the carbon felt electrodes prepared in the above Examples and Comparative Examples, and the results are shown in FIG.
도 3을 참조하면, 표면처리를 수행하지 않은 카본펠트 전극(도 3의 (a))의 경우, 젖음각이 99.66° 인 반면, 보론기 도입을 위한 표면처리가 수행된 카본펠트 전극(도3의 (b))의 경우, 젖음각이 85.54°인 것을 확인할 수 있다. 3, in the case of the carbon felt electrodes (Fig. 3 (a)) not subjected to the surface treatment, the carbon felt electrodes (Fig. 3 (B)), it can be seen that the wetting angle is 85.54 °.
이는 본 발명에 따른 표면처리법을 적용하여 카본펠트의 표면이 소수성에서 친수성으로 개질되었음을 의미한다.This means that the surface of the carbon felt is modified from hydrophobic to hydrophilic by applying the surface treatment method according to the present invention.
실험예 4: 카본펠트의 CV 측정Experimental Example 4: CV measurement of carbon felt
상기 실시예 및 상기 비교예에서 제조된 카본펠트 전극의 CV(cyclic voltammetry) 실험을 수행하였으며, 그 결과를 도 4에 도시하였다.A cyclic voltammetry (CV) experiment of the carbon felt electrodes prepared in the above Examples and Comparative Examples was performed, and the results are shown in FIG.
-0.7V ~ 1.3V에서 5mV/S의 전위주사속도(scan rate)로 CV 실험을 수행하였다. 기준 전극으로는 SCE (Saturated calomel electrode)를 사용하였으며 상대전극으로는 백금망을 사용하였다. 작업 전극(working electrode)으로는 실시예 및 비교예에서 제조한 카본펠트 전극을 직경 4mm 크기로 재단하여 사용하였다. 전해질은 1M의 황산(H2SO4)과 5mM 바나듐(V)의 혼합 수용액을 사용하였다.CV experiments were carried out at a potential scan rate of 5 mV / S at -0.7 V to 1.3 V. SCE (Saturated calomel electrode) was used as the reference electrode and platinum mesh was used as the counter electrode. As the working electrode, the carbon felt electrodes prepared in Examples and Comparative Examples were cut to a size of 4 mm in diameter and used. The electrolyte used was a mixed aqueous solution of 1 M sulfuric acid (H 2 SO 4 ) and 5 mM vanadium (V).
도 4를 참조하면, 표면처리를 수행하지 않은 카본펠트보다 본 발명에 따른 표면처리법을 적용한 카본펠트를 사용하는 경우 양/음극 반응성이 개선된 것을 확인할 수 있다. 이는 본 발명에 따른 표면처리법을 적용한 카본펠트 표면에 형성된 보론기가 바나듐 이온에 대한 활성화도가 크게 증가하였음을 나타낸다.Referring to FIG. 4, it can be seen that the positive / negative electrode reactivity is improved when the carbon felt to which the surface treatment method according to the present invention is applied is used than the carbon felt not subjected to the surface treatment. This indicates that the activity of the boron formed on the carbon felt surface to which the surface treatment method according to the present invention is applied is greatly increased with respect to the vanadium ion.
실험예 5: 카본펠트의 충방전 실험Experimental Example 5: Charge-discharge test of carbon felt
상기 실시예 및 상기 비교예에서 제조된 카본펠트 전극을 도 5에 도시된 단위셀의 구조에서의 전극으로 도입하고, 바이폴라 플레이트로는 흑연을, 이온교화막으로는 나피온을 도입한 후, 충방전을 실시하여 전압효율 및 에너지 효율 변화를 관찰하였으며, 그 결과를 도 6에 도시하고, 표 1에 정리하였다.The carbon felt electrode prepared in the above Examples and Comparative Examples was introduced into the electrode in the structure of the unit cell shown in Fig. 5, graphite was introduced into the bipolar plate, Nafion was introduced into the ion exchange membrane, And the voltage efficiency and the energy efficiency were observed. The results are shown in FIG. 6 and summarized in Table 1.
도 6을 참조하면, 상기 실시예의 전극이 비교예의 전극보다 에너지 효율이 크게 증가한 것을 확인할 수 있으며, 이는 카본펠트 표면에 형성된 보론기로 인해 바나듐 이온에 대한 활성화도가 크게 증가하였음을 나타낸다.Referring to FIG. 6, it can be seen that the energy efficiency of the electrode of the above embodiment is significantly increased compared to that of the electrode of the comparative example. This indicates that the activity of the vanadium ion is greatly increased due to the boron formed on the carbon felt surface.
| Coulomb(%)Coulomb (%) | Voltagev(%)Voltagev (%) | Energy(%)Energy (%) | |
| 3F-bare(비교예)3F-bare (comparative example) | 94.5194.51 | 86.7986.79 | 82.0382.03 |
| 2M NH4BF4(실시예)2M NH 4 BF 4 (Example) | 94.5394.53 | 91.7791.77 | 86.7586.75 |
이상, 본 발명내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적인 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의해 정의된다고 할 것이다.Having described specific portions of the present invention in detail, those skilled in the art will appreciate that these specific embodiments are merely preferred embodiments and that the scope of the present invention is not limited thereby. something to do. Accordingly, the actual scope of the present invention will be defined by the appended claims and their equivalents.
Claims (8)
- 표면에 보론기가 도입된 카본펠트.Carbon felt with boron introduced on its surface.
- 제 1 항에 있어서,The method according to claim 1,상기 카본펠트는 망상구조인 것을 특징으로 하는 카본펠트.Wherein the carbon felt has a network structure.
- 제 1 항에 있어서, The method according to claim 1,상기 카본 펠트는 젖음각이 90°이하인 것인 Wherein the carbon felt has a wiping angle of 90 DEG or less카본펠트 Carbon felt
- 제 1 항 내지 제 3 항 중 어느 한 항의 카본펠트를 포함하는 레독스 플로우 이차전지용 전극.An electrode for a redox flow secondary battery comprising the carbon felt according to any one of claims 1 to 3.
- 제 4 항에 의한 전극을 포함하는 레독스 플로우 전지.A redox flow battery comprising an electrode according to claim 4.
- (a) 보론 전구체 용액에 카본펠트를 담지한 후 건조시키는 단계; 및(a) carrying carbon felt on a boron precursor solution and drying the carbon felt; And(b) 상기 담지된 카본펠트를 열처리하는 단계;를 포함하는(b) heat treating the supported carbon felt카본펠트 표면처리 방법.Method for surface treatment of carbon felt.
- 제 6 항에 있어서,The method according to claim 6,상기 보론 전구체는 NH4BF4, NaBH4, KBH4, LiBH4, B2H6, B(CH3)3 또는 TEB로 구성된 군으로부터 선택되는 1종 이상인 것인The boron precursor may be NH 4 BF 4 , NaBH 4 , KBH 4 , LiBH 4 , B 2 H 6 , B (CH 3 ) 3, or TEB.카본펠트 표면처리 방법.Method for surface treatment of carbon felt.
- 제 6 항에 있어서,The method according to claim 6,상기 열처리하는 단계에서는 700 내지 1000 ℃ 에서 열처리하는 것인In the heat treatment step, the heat treatment is performed at 700 to 1000 ° C.카본펠트 표면처리 방법.Method for surface treatment of carbon felt.
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| US20140127542A1 (en) * | 2012-11-05 | 2014-05-08 | Battelle Memorial Institute | Composite Separators and Redox Flow Batteries Based on Porous Separators |
| KR20170043113A (en) * | 2015-10-12 | 2017-04-21 | 전자부품연구원 | Carbon felt for vanadium redox flow secondary battery, and method for manufacturing the same |
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| US20140127542A1 (en) * | 2012-11-05 | 2014-05-08 | Battelle Memorial Institute | Composite Separators and Redox Flow Batteries Based on Porous Separators |
| KR20170043113A (en) * | 2015-10-12 | 2017-04-21 | 전자부품연구원 | Carbon felt for vanadium redox flow secondary battery, and method for manufacturing the same |
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| Title |
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| KIM, KI JAE ET AL.: "Superior Electrocatalytic Activity of a Robust Carbon-felt Electrode with Oxygen-rich Phosphate Groups for All-vanadium Redox Flow Batteries", CHEMSUSCHEM, vol. 9, no. 11, 2016, pages 1329 - 1338, XP055623318 * |
| RYU, JAECHAN ET AL.: "Catalytic Effects of B/N-co-doped Porous Carbon Incorporated with Ketjenblack Nanoparticles for All-vanadium Redox Flow Batteries", JOURNAL OF T H E ELECTROCHEMICAL SOCIETY, vol. 163, no. 1, 2016, pages A5144 - A5149, XP055610260, doi:10.1149/2.0191601jes * |
| SOGABE, T. ET AL.: "Effect of Boron-doping on Structure and Some Properties of Carbon-carbon Composite", JOURNAL OF MATERIALS SCIENCE, vol. 31, no. 24, 1996, pages 6469 - 6476, XP055623312 * |
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