미세다공성 RuO<sub>2</sub>-ZrO<sub>2</sub> 복합 금속 산화물 전극의 제조

이강만; 황규연; 고희찬; 여태환; Kangman Lee; Kyuyeun Hwang; Heechan Ko; Taewhan Yeu

HWAHAK KONGHAK, Vol.38, No.3, 405-410, June, 2000

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미세다공성 RuO₂-ZrO₂ 복합 금속 산화물 전극의 제조

The Preparation of Microporous RuO₂-ZrO₂ Mixed Metal Oxide Electrodes

이강만, 황규연, 고희찬¹, 여태환 ^{1, †}

중앙대학교 화학공학과, 서울 156-756
¹한화그룹종합연구소 신소재연구센터, 대전 305-345

Kangman Lee, Kyuyeun Hwang, Heechan Ko¹, and Taewhan Yeu^{1, †}

Department of Chemical Engineering, Chung-Ang University, 221 Huksuk-Dong, Dongjak-Ku, Seoul 156-756, Korea
¹Department of Chemical Engineering, Hanwha Group R&E Center, 6 Shinsung-Dong, Yusong-Ku, Taejon 305-345, Korea

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초록

Zirconium propoxide를 전구체로 하고 질산을 안정화제로 하여 건조조절제 없이 졸-겔 공정으로 Zr(OCH₂CH₂CH₃)₄:C₂H₅OH:H₂O:HNO₃=1:50:4:0.16의 조성에서 안정하고 균질한 ZrO₂ 졸을 얻었으며 dipping법으로 티타늄 기판 위에 코팅하고 450℃에서 열처리하여 RuO₂-ZrO₂/Ti 복합 금속 산화물 전극을 제조하였다. XRD 분석으로 ZrO₂는 tetragonal 구조이고 RuO₂는 rutile 구조임을 확인할 수 있었으며 복합 금속 산화물에서 RuO₂와 ZrO₂의 intensity는 각각의 조성에 비례하였다. ZrO₂의 첨가로 비표면적이 증가하였으며, 40%이상의 RuO₂를 함유하는 복합 금속 산화물 전극에서는 균열을 발견할 수 없었다. 40%의 RuO₂를 함유하는 RuO₂-ZrO₂/Ti 복합 금속 산화물 전극에서 열분해법으로 얻은 RuO₂/Ti 전극에 비하여 높은 비표면적과 함께 산소 발생 반응에 대하여 상대적으로 높은 교환 전류 밀도와 낮은 과전압을 얻을 수 있었다.

Without drying control chelating agent, stable and uniform zirconia sol was obtained at Zr(OCH₂CH₂CH₃)₄:C₂H₅OH:H₂O:HNO₃=1:50:4:0.16. RuO₂-ZrO₂/Ti mixed metal oxide electrodes were obtained by dip-coating on titanium substrate. The X-ray diffraction patterns of metal oxides fired at 450℃ conformed a tetragonal-type ZrO₂ and a rutile-type RuO₂ regardless of oxide composition. Intensity of XRD varied linearly with oxide compositions. By addition of ZrO₂ the specific surface area increased. Mixed metal oxide electrodes containing RuO₂ more than 40% exhibited no crack and uniform coating surface. The mixed metal oxide electrode containing 40% RuO₂ showed higher exchange current density and lower overpotential for the oxygen evolution with higher specific surface area compared to RuO₂/Ti electrode prepared by a thermal decomposition.

Keywords:Metal Oxide Electrode;Zirconium Oxide;Ruthenium Oxide;Sol-gel;Chloro-alkali;Chelating Agent

[References]

Beer HB, U.S. Patent, 549,194 (1966)
Beer HB, U.S. Patent, 3,632,498 (1972)
Beer HB, U.S. Patent, 3,711,385 (1973)
Trasatti S, "Electrode of Conductive Metallic Oxide," Elsevier Scientific Publishing Company, New York (1980)
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Tanabe K, Mat. Chem. Phys., 13, 347 (1985)
Hammett A, Stevens P, Troughton GL, Catal. Today, 7, 219 (1990)
Ardizzone S, Bassi G, Mat. Chem. Phys., 25, 417 (1990)
Randon J, Larbot A, Guizard C, Cot L, Lindheimer M, Partyka S, Colloid Surf., 52, 241 (1991)
Comninellis C, Vercesi GP, J. Appl. Electrochem., 21, 335 (1991)
Subramanian K, Guruviah S, Bull. Electrochem., 2, 561 (1986)
Kim BH, Hong K, Shin DW, J. Korean Ceram. Soc., 31, 1060 (1994)
Hwang K, Ko H, Yeu T, HWAHAK KONGHAK, 37(5), 725 (1999)
Bard AJ, Faulkner LR, "Electrochemical Methods Fundamentals and Applications," John Wiley & Sons, New York (1980)

[Related Articles]

[1] Beer HB, U.S. Patent, 549,194 (1966)

[2] Beer HB, U.S. Patent, 3,632,498 (1972)

[3] Beer HB, U.S. Patent, 3,711,385 (1973)

[4] Trasatti S, "Electrode of Conductive Metallic Oxide," Elsevier Scientific Publishing Company, New York (1980)

[5] Yoldas BE, J. Mater. Sci., 10, 1856 (1975)

[6] Burke LD, McCarthy M, Electrochim. Acta, 29, 211 (1984)

[7] Guglielmi M, J. Electrochem. Soc., 139, 1655 (1992)

[8] Kameyama K, Shohji S, Onoue S, Nishimura K, Yahikozawa K, Takasu Y, J. Electrochem. Soc., 140, 1034 (1993)

[9] Camara OR, Trasatti S, Electrochim. Acta, 41(3), 419 (1996)

[10] Boodts JFC, Trasatti S, J. Electrochem. Soc., 137, 3784 (1990)

[11] Kameyama K, Tsukada K, Yahikozawa K, Takasu Y, J. Electrochem. Soc., 141(3), 643 (1994)

[12] Tanabe K, Mat. Chem. Phys., 13, 347 (1985)

[13] Hammett A, Stevens P, Troughton GL, Catal. Today, 7, 219 (1990)

[14] Ardizzone S, Bassi G, Mat. Chem. Phys., 25, 417 (1990)

[15] Randon J, Larbot A, Guizard C, Cot L, Lindheimer M, Partyka S, Colloid Surf., 52, 241 (1991)

[16] Comninellis C, Vercesi GP, J. Appl. Electrochem., 21, 335 (1991)

[17] Subramanian K, Guruviah S, Bull. Electrochem., 2, 561 (1986)

[18] Kim BH, Hong K, Shin DW, J. Korean Ceram. Soc., 31, 1060 (1994)

[19] Hwang K, Ko H, Yeu T, HWAHAK KONGHAK, 37(5), 725 (1999)

[20] Bard AJ, Faulkner LR, "Electrochemical Methods Fundamentals and Applications," John Wiley & Sons, New York (1980)