이온교환막을 이용한 이온의 분리특성에 관한 연구 I.전바나듐계 레독스-흐름 전지의 격막용 이온 교환막의 특성

강안수

Journal of the Korean Industrial and Engineering Chemistry, Vol.4, No.2, 393-402, June, 1993

The Study on the Separation Characteristics of ion with ion Exchange Membrane-1.The Characteristics of ion Exchange Membrane with the Separator of All-Vanadium Redox Flow Battery-

강안수

초록

레독스-흐름 2차전지는 발전소의 잉여 전력, 태양전지 및 전기자동차 등 응용분야가 넓은 유망한 에너지 저장 방법의 하나이다. 활성물질로소 바나듐-황산 수용액을 이용하는 전바나듐 레독스-흐름 전지에서 효율적인 이온 선택 성막의 개발은 아직도 문제점으로 남아 있다. 전바나듐 레독스-흐름 전지용 격막으로서 기초막에 UV를 조사하면서 30분간 chlorosulfonation 시킨 비대칭 양이온 교환막(M-30)이 운반율 0.94 막저항 0.5Ω·㎝²로 가장 좋았다. 기초막은 pololefin막(HIPORE 1200)에 10㎛두께의 저밀도 폴리에틸렌 막을 접착시켜 제조되었다. 실제 바나듐-황산 수용액에서의 막저항도 3.79Ω·㎝²로 Nafion 117막과 비슷하였고, 셀저항율도 6.6Ω·㎝²로 Nafion 117막보다 낮았다. 막의 전기화학적 물성치와 가격 등을 고려할 때 전바나듐 레독스-흐름 전지의 격막으로서 M-30막이 Nafion 117막과 Asahi초자의 CMV막보다 우수하였다.

Redox flow secondary battery have been studied actively as one of the most promising electrochemical energy storage devices for a wide range of applications, such as electric vehicles, photovoltaic arrays, and excess power generated by electric power plants. In all-vanadium redox flow battery using solution of vanadium-sulfuric acid as a active material, the difficulty in developing an efficient ion selective membrane can still be identified. The asymmetric cation exchange membrane(M-30) as a separator of all-vanadium redox flow battery which were obtained by the reaction of chlorosulfonation for 30 minutes under the irradiation of UV, showed its superiority in the transport number of 0.94 and electrical resistivity of 0.5Ω·㎝². The base membrane were prepared by lamination a low density polyethlene film of 10㎛ thickness on polyolefin membrane(HIPORE 120). The electrical resistivity of M-30 membrane in real solution of vanadium-sulfuric acid was 3.79Ω·㎝² and it was similar to that of Nafion 117 membrane. Also the cell resistivity was 6.6Ω·㎝² and lower than that of Nafion 117. In considertion of electrochemical properties and costs of membranes, M-30 membrane was better than that of Nafion 117 and CMV of Asahi glass Co. as a separator of all-vanadium redox flow battery.

[References]

Gahn N, Hagedorn H, Ling JS, "Single Cell Performance on the Fe/Cr Redox Energy Stoage System Using Mixed Reactant Solutions at Elevated Temperature," NASA TM-83385 (1983)
Skllas-kazacos M, Kasherman D, Hong DR, Kazacos M, J. Power Sources, 35, 399 (1991)
Kaneko H, Nozaki K, Wada Y, Aoki T, Negish A, Kamimoto M, Electrochim. Acta, 36, 1191 (1991)
Pourbaix M, "Atlas of Electrochemical Equilibria in Aqueous Solutions," National Association of Corrosion Engineers, Houston (1982)
Thaller LH, "Electrically Rechargeable Redox Flow Cells," Proc. 19th IECEC, p. 924 (1984)
Nozaki K, Kaneko H, Negishi A, Ozawa T, Denki Kagaku, 51, 189 (1983)
Rychcik M, Skyllas M, J. Power Sources, 22, 59 (1988)
Sum E, Rychik M, Skyllas-Kazacos M, J. Power Sources, 16, 85 (1985)
Larsson R, Folkesson B, J. Appl. Electrochem., 20, 737 (1990)
Oei DG, J. Appl. Electrochem., 15, 231 (1985)
Lacey RE, Cowasr DR, "Development of Anion-Selective Membranes," NASA CR-134 932 (1975)
Alexander SS, Hodgedon RB, Waite WA, "Anion Permselective Membranes," NASA CA-159 599 (1977)
Ohya H, Emori K, Ohto T, Negish Y, Denki Kagaku, 52, 341 (1984)
Ohya H, Ohto T, Sawamura T, Honda H, Matsumoto K, Negish Y, Denki Kagaku, 56, 34 (1988)
Ohya H, Haio A, Kuromoto M, Matsumoto K, Negish Y, Denki Kagaku, 58, 1021 (1990)
deKorosy F, Shorr J, "Preparation and Poisoning of Permselective Membranes," Dechema Mogr., 47, 477-486 (1992)
Jagu-Grodzinski J, Bikson B, Vofsi D, "Ionically Charged Tubular Membranes for Water Softening and Desalination," 4th Inter. Symp. on Fresh Water from the Sea, Vol. 4, 171-180 (1973)
Kirllov AN, Plast. Massy, 8, 54 (1997)
Ogiwara Y, Kanda M, Takumi N, Kuboa H, J. Polym. Sci. C: Polym. Lett., 19, 457 (1981)
Lehoussel J, Wattiez D, Marechal E, Eur. Polym. J., 15, 915 (1979)
Kharasch MS, Chad TH, Brown HC, J. Am. Chem. Soc., 61, 3089 (1939)
Subrahmayan V, Lakshminarayanaiah, J. Phys. Chem., 72, 4314 (1968)
Berzins T, "Electrochemical Charterization of Nafion Membranes in Chlor-Alkali Cells," Electrochem. Soc. Fall Meeting, Atlanta, U.S.A. (1977)
Jobst K, Sawtschenko L, Wuckel L, Plaste Kautschuk., 13, 579 (1966)
Sata T, Izuo R, Takata K, J. Membr. Sci., 45, 197 (1989)

[Referenced By]

[1] Gahn N, Hagedorn H, Ling JS, "Single Cell Performance on the Fe/Cr Redox Energy Stoage System Using Mixed Reactant Solutions at Elevated Temperature," NASA TM-83385 (1983)

[2] Skllas-kazacos M, Kasherman D, Hong DR, Kazacos M, J. Power Sources, 35, 399 (1991)

[3] Kaneko H, Nozaki K, Wada Y, Aoki T, Negish A, Kamimoto M, Electrochim. Acta, 36, 1191 (1991)

[4] Pourbaix M, "Atlas of Electrochemical Equilibria in Aqueous Solutions," National Association of Corrosion Engineers, Houston (1982)

[5] Thaller LH, "Electrically Rechargeable Redox Flow Cells," Proc. 19th IECEC, p. 924 (1984)

[6] Nozaki K, Kaneko H, Negishi A, Ozawa T, Denki Kagaku, 51, 189 (1983)

[7] Rychcik M, Skyllas M, J. Power Sources, 22, 59 (1988)

[8] Sum E, Rychik M, Skyllas-Kazacos M, J. Power Sources, 16, 85 (1985)

[9] Larsson R, Folkesson B, J. Appl. Electrochem., 20, 737 (1990)

[10] Oei DG, J. Appl. Electrochem., 15, 231 (1985)

[11] Lacey RE, Cowasr DR, "Development of Anion-Selective Membranes," NASA CR-134 932 (1975)

[12] Alexander SS, Hodgedon RB, Waite WA, "Anion Permselective Membranes," NASA CA-159 599 (1977)

[13] Ohya H, Emori K, Ohto T, Negish Y, Denki Kagaku, 52, 341 (1984)

[14] Ohya H, Ohto T, Sawamura T, Honda H, Matsumoto K, Negish Y, Denki Kagaku, 56, 34 (1988)

[15] Ohya H, Haio A, Kuromoto M, Matsumoto K, Negish Y, Denki Kagaku, 58, 1021 (1990)

[16] deKorosy F, Shorr J, "Preparation and Poisoning of Permselective Membranes," Dechema Mogr., 47, 477-486 (1992)

[17] Jagu-Grodzinski J, Bikson B, Vofsi D, "Ionically Charged Tubular Membranes for Water Softening and Desalination," 4th Inter. Symp. on Fresh Water from the Sea, Vol. 4, 171-180 (1973)

[18] Kirllov AN, Plast. Massy, 8, 54 (1997)

[19] Ogiwara Y, Kanda M, Takumi N, Kuboa H, J. Polym. Sci. C: Polym. Lett., 19, 457 (1981)

[20] Lehoussel J, Wattiez D, Marechal E, Eur. Polym. J., 15, 915 (1979)

[21] Kharasch MS, Chad TH, Brown HC, J. Am. Chem. Soc., 61, 3089 (1939)

[22] Subrahmayan V, Lakshminarayanaiah, J. Phys. Chem., 72, 4314 (1968)

[23] Berzins T, "Electrochemical Charterization of Nafion Membranes in Chlor-Alkali Cells," Electrochem. Soc. Fall Meeting, Atlanta, U.S.A. (1977)

[24] Jobst K, Sawtschenko L, Wuckel L, Plaste Kautschuk., 13, 579 (1966)

[25] Sata T, Izuo R, Takata K, J. Membr. Sci., 45, 197 (1989)