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Received July 18, 2019
Accepted August 24, 2019
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수계 유기 레독스 흐름 전지 성능에서의 첨가제 효과
The Effect of Additives on the Performance of Aqueous Organic Redox Flow Battery Using Quinoxaline and Ferrocyanide Redox Couple
서울과학기술대학교 에너지환경대학원, 01811 서울특별시 노원구 공릉로 232
Graduate school of Energy and Environment, Seoul National University of Science and Technology, 232 Gongneung-ro, Nowon-gu, Seoul, 01811, Korea
Korean Chemical Engineering Research, December 2019, 57(6), 847-852(6), 10.9713/kcer.2019.57.6.847 Epub 3 December 2019
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Abstract
본 연구에서는 퀴노잘린(quinoxaline)과 페로시아나이드(ferrocyanide)를 활물질로 활용한 알칼리 전해질 기반 수계유기 레독스 흐름전지에 대해 다양한 첨가제를 적용하여 성능을 비교하는 실험을 진행하였다. 퀴노잘린(quinoxaline)의 경우 염화칼륨(KCl) 전해질보다는 수산화칼륨(KOH) 전해질에서의 레독스 전위(-0.97 V)가 더 작은 위치에 있으며, 이에따라 KOH 전해질에 대해 페로시아나이드와 조합을 이루었을 때, 셀 전압 값은 1.3 V로 높게 나타났다. 상용 양이온 교환막 중 하나인 Nafion 117 멤브레인을 사용하였을 때, 퀴노잘린(quinoxaline)의 부반응 현상을 반전지 상에서 관찰 할 수 있었으며, 이에 따라 충방전 자체가 잘 되지 않는 문제점이 있다. 따라서, 문제점이 되는 퀴노잘린(quinoxaline)의 부반응을 해결하기 위해 친전자체와 친핵체 중 하나인 포타슘설페이트(K2SO4)와 포타슘아이오다이드(KI)를 사용하였으며, 포타슘아이오다이드(KI)를 사용하였을 때, 용량 손실율 측면에서 포타슘 아이오다이드(KI)를 첨가제로 넣지 않았을 때(0.29 Ah·L-1 per cycle) 보다 더 낮은 용량 손실율(0.21 Ah·L-1 per cycle)로 더 높은 용량 유지율을 보였다.
In this study, the effect of additives on the performance of aqueous organic redox flow battery (AORFB) using quinoxaline and ferrocyanide as active materials in alkaline supporting electrolyte is investigated. Quinoxaline shows the lowest redox potential (-0.97 V) in KOH supporting electrolyte, while when quinoxaline and ferrocyanide are used as the target active materials, the cell voltage of this redox combination is 1.3 V. When the single cell tests of AORFBs using 0.1 M active materials in 1 M KCl supporting electrolyte and Nafion 117 membrane are implemented, it does not work properly because of the side reaction of quinoxaline. To reduce or prevent the side reaction of quinoxaline, the two types of additives are considered. They are the potassium sulfate as electrophile additive and potassium iodide as nucleophilie additive. Of them, when the single cell tests of AORFBs using potassium iodide as additive dissolved in quinoxaline solution are performed, the capacity loss rate is reduced to 0.21 Ah·L-1 per cycle and it is better than that of the single cell test of AORFB operated without additive (0.29 Ah·L-1 per cycle).
Keywords
References
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Noh C, Lee CS, Chi WS, Chung Y, Kim JH, Kwon Y, J. Electrochem. Soc., 165(7), A1388 (2018)
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Chang ZJ, Henkensmeier D, Chen RY, J. Power Sources, 418, 11 (2019)
Chen Q, Gerhardt MR, Hartle L, Aziz MJ, J. Electrochem. Soc., 163(1), A5010 (2016)
Lin K, Gomez-Bombarelli R, Beh ES, Tong L, Chen Q, Valle A, Aspuru-Guzik A, Aziz MJ, Gordon RG, Nat. Energy, 1, 16102 (2016)
Agmon N, Chem. Phys. Lett., 319(3-4), 247 (2000)
Milshtein JD, Su L, Liou C, Badel AF, Brushett FR, Electrochim. Acta, 180, 695 (2015)
Luo J, Sam A, Hu B, DeBruler C, Wei X, Wang W, Liu TL, Nano Energy, 42, 215 (2017)
Badr MZA, El-Naggar GM, El-Sherief HAH, Abdel-Rahman AES, Aly MF, Bull. Chem. Soc. Jpn., 56, 326 (1983)
Aleksic MM, Pantic J, Kapetanovic VP, Facta Univer. Ser. Phys. Chem. Technol., 12, 55 (2014)
Nagarajan R, Perumal PT, Chem. Lett., 33(3), 288 (2004)
Mabbott GA, J. Chem. Educ., 60, 697 (1983)
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Altshuller AP, Schwab CM, Bare M, Anal Chem, 31, 1987 (1959)
Chakrabarti MH, Dryfe RAW, Roberts EPL, Electrochim. Acta, 52(5), 2189 (2007)