Quantitative Evaluation of the Activity of Low-Spin Tetravalent Nickel Ion Sites for the Oxygen Evolution ReactionClick to copy article linkArticle link copied!
- Yadan RenYadan RenGraduate School of Human and Environmental Studies, Kyoto University, Yoshida Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, JapanMore by Yadan Ren
- Tomoya HoriguchiTomoya HoriguchiGraduate School of Human and Environmental Studies, Kyoto University, Yoshida Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, JapanMore by Tomoya Horiguchi
- Tomoki Uchiyama*Tomoki Uchiyama*Email: [email protected]Graduate School of Human and Environmental Studies, Kyoto University, Yoshida Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, JapanMore by Tomoki Uchiyama
- Yuki OrikasaYuki OrikasaDepartment of Applied Chemistry, College of Life Sciences, Ritsumeikan University, 1-1-1 Noji Higashi, Kusatsu, Shiga 535-8577, JapanMore by Yuki Orikasa
- Toshiki WatanabeToshiki WatanabeGraduate School of Human and Environmental Studies, Kyoto University, Yoshida Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, JapanMore by Toshiki Watanabe
- Kentaro YamamotoKentaro YamamotoGraduate School of Human and Environmental Studies, Kyoto University, Yoshida Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, JapanMore by Kentaro Yamamoto
- Tsuyoshi TakamiTsuyoshi TakamiGraduate School of Human and Environmental Studies, Kyoto University, Yoshida Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, JapanMore by Tsuyoshi Takami
- Toshiyuki MatsunagaToshiyuki MatsunagaGraduate School of Human and Environmental Studies, Kyoto University, Yoshida Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, JapanMore by Toshiyuki Matsunaga
- Yoshinori NishikiYoshinori NishikiDe Nora Permelec Ltd, 2023-15 Endo, Fujisawa-shi, Kanagawa 252-0816, JapanMore by Yoshinori Nishiki
- Shigenori MitsushimaShigenori MitsushimaGraduate School of Engineering Science, Yokohama National University, 79-5, Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa 240-8501, JapanInstitute of Advanced Sciences, Yokohama National University, 79-5, Tokiwadai, Hodogaya-ku, Yokohama, Kanagawa 240-8501, JapanMore by Shigenori Mitsushima
- Yoshiharu UchimotoYoshiharu UchimotoGraduate School of Human and Environmental Studies, Kyoto University, Yoshida Nihonmatsu-cho, Sakyo-ku, Kyoto 606-8501, JapanMore by Yoshiharu Uchimoto
Abstract
Oxide catalysts containing tetravalent nickel exhibit high oxygen-active catalytic activity. We investigated the effects of lithium content (x) on the electrocatalytic activity of LixNi0.5Mn1.5O4, a spinel that provides only divalent and tetravalent nickel ions in a KOH aqueous electrolyte for the oxygen evolution reaction (OER). The lithium content was controlled by the chemical delithiation of Li0.96Ni0.49Mn1.51O4 using NO2BF4. Upon employing this approach, nickel changed from the divalent to tetravalent state. The OER activity increased with decreasing x, and a higher activity than that of standard LaNiO3 was observed at x = 0.00. Comprehensive Tafel analyses and X-ray spectroscopic investigations revealed a downshift in the Ni conduction band, indicating that high OER activity correlated with strong hybridization of the Ni 3d and O 2p orbitals. These insights into the role of Ni4+ in high OER activity are expected to facilitate the development of other highly active Ni-based electrocatalysts.
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