Rotating ring-disk studies of oxidized nickel hydrous oxide: Oxygen evolution and pseudocapacitance

Yining Hu, Yuriy V. Tolmachev, Daniel Alberto Scherson

Research output: Contribution to journalConference article

31 Citations (Scopus)

Abstract

A rotating ring-disk electrode (RRDE) method is herein described for studies of O2 evolution on nickel hydrous oxide films, NiOx(hydr.), electrodeposited on the gold disk of a Au-Au RRDE in aqueous 1.0 M KOH. This technique relies on the quantitative detection of O2 generated at the NiOx(hydr.)|Au disk electrode during a linear potential scan, by the concentric, bare Au-ring electrode, which can then be used to determine contributions to the disk current (Idisk) derived solely from O2 evolution. Subtraction of such contributions from Idisk in the potential range positive to the trailing edge of the peak ascribed to the oxidation of the NiOx(hydr.) film revealed a constant, positive current when the voltage was scanned in the positive direction, and a constant, negative current, albeit of smaller magnitude, in the subsequent scan in the negative direction. This observation suggests that once account is made for O2 evolution, the NiOx(hydr.)|Au-electrolyte interface in that potential range (0.5-0.65 V vs. Hg|HgO,OH-), behaves as a (pseudo) capacitor, a model that was further confirmed by monitoring the current as a function of the scan rate. The actual values of this pseudocapacitance were found to be on the order of ca. 80 kF mol-1 Ni sites in the film (or equivalently, ca. 0.1 e- per Ni site within the potential range specified above) and, thus, very similar to those reported earlier based on current interruption-potential decay and impedance measurements for O2 evolution on NiOx(hydr.) grown on Ni electrodes. Implications of these results to the mechanism of self-discharge of NiOx(hydr.) electrodes for alkaline secondary batteries are discussed.

Original languageEnglish
Pages (from-to)64-69
Number of pages6
JournalJournal of Electroanalytical Chemistry
Volume468
Issue number1
DOIs
Publication statusPublished - 1999 Jun 17
Externally publishedYes
EventProceedings of the 1998 International Symposium on New Trends in Electroanalytical Chemistry - Seoul, S Kor
Duration: 1998 Sep 101998 Sep 12

Fingerprint

Nickel oxide
Oxygen
Electrodes
Secondary batteries
Gold
Electrolytes
Oxide films
nickel monoxide
Capacitors
Oxidation
Monitoring
Electric potential

ASJC Scopus subject areas

  • Analytical Chemistry
  • Chemical Engineering(all)
  • Electrochemistry

Cite this

Rotating ring-disk studies of oxidized nickel hydrous oxide : Oxygen evolution and pseudocapacitance. / Hu, Yining; Tolmachev, Yuriy V.; Scherson, Daniel Alberto.

In: Journal of Electroanalytical Chemistry, Vol. 468, No. 1, 17.06.1999, p. 64-69.

Research output: Contribution to journalConference article

Hu, Yining ; Tolmachev, Yuriy V. ; Scherson, Daniel Alberto. / Rotating ring-disk studies of oxidized nickel hydrous oxide : Oxygen evolution and pseudocapacitance. In: Journal of Electroanalytical Chemistry. 1999 ; Vol. 468, No. 1. pp. 64-69.
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N2 - A rotating ring-disk electrode (RRDE) method is herein described for studies of O2 evolution on nickel hydrous oxide films, NiOx(hydr.), electrodeposited on the gold disk of a Au-Au RRDE in aqueous 1.0 M KOH. This technique relies on the quantitative detection of O2 generated at the NiOx(hydr.)|Au disk electrode during a linear potential scan, by the concentric, bare Au-ring electrode, which can then be used to determine contributions to the disk current (Idisk) derived solely from O2 evolution. Subtraction of such contributions from Idisk in the potential range positive to the trailing edge of the peak ascribed to the oxidation of the NiOx(hydr.) film revealed a constant, positive current when the voltage was scanned in the positive direction, and a constant, negative current, albeit of smaller magnitude, in the subsequent scan in the negative direction. This observation suggests that once account is made for O2 evolution, the NiOx(hydr.)|Au-electrolyte interface in that potential range (0.5-0.65 V vs. Hg|HgO,OH-), behaves as a (pseudo) capacitor, a model that was further confirmed by monitoring the current as a function of the scan rate. The actual values of this pseudocapacitance were found to be on the order of ca. 80 kF mol-1 Ni sites in the film (or equivalently, ca. 0.1 e- per Ni site within the potential range specified above) and, thus, very similar to those reported earlier based on current interruption-potential decay and impedance measurements for O2 evolution on NiOx(hydr.) grown on Ni electrodes. Implications of these results to the mechanism of self-discharge of NiOx(hydr.) electrodes for alkaline secondary batteries are discussed.

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