skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Determination of the “NiOOH” charge and discharge mechanisms at ideal activity

Abstract

Here, optimization of electrodeposition conditions produced Ni(OH)2 deposits chargeable up to 1.84 ± 0.02 e per Ni on and the resulting nickel oxide/hydroxide active material could subsequently deliver 1.58 ± 0.02 e per Ni ion (462 mA h/g) over a potential range <0.2 V. The ability of the “NiOOH” active material to deliver an approximately ideal charge and discharge facilitated a coulometric and thermodynamic analysis through which the charge/discharge mechanisms were determined from known enthalpies of formation. The (dis)charge states were confirmed with in situ Raman spectroscopy. The mechanisms were additionally evaluated with respect to pH and potential dependence, charge quantities, hysteresis, and fluoride ion partial inhibition of the charge mechanism. The results indicate that the “NiOOH” (dis)charges as a solid-state system with mechanisms consistent with known nickel and oxygen redox reactions. A defect chemistry mechanism known for the LiNiO2 system also occurs for “NiOOH” to cause both high activity and hysteresis. Similar to other cation insertion nickel oxides, the activity of the “NiOOH” mechanism is predominantly due to oxygen redox activity and does not involve the Ni4+ oxidation state. The “NiOOH” was produced from cathodic electrodeposition of Ni(OH)2 from nickel nitrate solutions onto highly oriented pyrolytic graphite at idealmore » electrodeposition current efficiencies and the deposition mechanism was also characterized.« less

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Chemical Sciences Div.
Publication Date:
Research Org.:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1305895
Report Number(s):
LLNL-JRNL-539131
Journal ID: ISSN 1572-6657
Grant/Contract Number:  
AC52-07NA27344
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Electroanalytical Chemistry
Additional Journal Information:
Journal Volume: 717-718; Journal Issue: C; Journal ID: ISSN 1572-6657
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
30 DIRECT ENERGY CONVERSION; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; NiOOH; Ni(OH)2; nickel electrode; nickel oxy-hydroxide; active oxygen

Citation Formats

Merrill, Matthew, Worsley, Marcus, Wittstock, Arne, Biener, Juergen, and Stadermann, Michael. Determination of the “NiOOH” charge and discharge mechanisms at ideal activity. United States: N. p., 2014. Web. doi:10.1016/j.jelechem.2014.01.022.
Merrill, Matthew, Worsley, Marcus, Wittstock, Arne, Biener, Juergen, & Stadermann, Michael. Determination of the “NiOOH” charge and discharge mechanisms at ideal activity. United States. https://doi.org/10.1016/j.jelechem.2014.01.022
Merrill, Matthew, Worsley, Marcus, Wittstock, Arne, Biener, Juergen, and Stadermann, Michael. 2014. "Determination of the “NiOOH” charge and discharge mechanisms at ideal activity". United States. https://doi.org/10.1016/j.jelechem.2014.01.022. https://www.osti.gov/servlets/purl/1305895.
@article{osti_1305895,
title = {Determination of the “NiOOH” charge and discharge mechanisms at ideal activity},
author = {Merrill, Matthew and Worsley, Marcus and Wittstock, Arne and Biener, Juergen and Stadermann, Michael},
abstractNote = {Here, optimization of electrodeposition conditions produced Ni(OH)2 deposits chargeable up to 1.84 ± 0.02 e– per Ni on and the resulting nickel oxide/hydroxide active material could subsequently deliver 1.58 ± 0.02 e– per Ni ion (462 mA h/g) over a potential range <0.2 V. The ability of the “NiOOH” active material to deliver an approximately ideal charge and discharge facilitated a coulometric and thermodynamic analysis through which the charge/discharge mechanisms were determined from known enthalpies of formation. The (dis)charge states were confirmed with in situ Raman spectroscopy. The mechanisms were additionally evaluated with respect to pH and potential dependence, charge quantities, hysteresis, and fluoride ion partial inhibition of the charge mechanism. The results indicate that the “NiOOH” (dis)charges as a solid-state system with mechanisms consistent with known nickel and oxygen redox reactions. A defect chemistry mechanism known for the LiNiO2 system also occurs for “NiOOH” to cause both high activity and hysteresis. Similar to other cation insertion nickel oxides, the activity of the “NiOOH” mechanism is predominantly due to oxygen redox activity and does not involve the Ni4+ oxidation state. The “NiOOH” was produced from cathodic electrodeposition of Ni(OH)2 from nickel nitrate solutions onto highly oriented pyrolytic graphite at ideal electrodeposition current efficiencies and the deposition mechanism was also characterized.},
doi = {10.1016/j.jelechem.2014.01.022},
url = {https://www.osti.gov/biblio/1305895}, journal = {Journal of Electroanalytical Chemistry},
issn = {1572-6657},
number = C,
volume = 717-718,
place = {United States},
year = {Fri Jan 24 00:00:00 EST 2014},
month = {Fri Jan 24 00:00:00 EST 2014}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 54 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Environmentally Friendly Nickel-Zinc Battery for High Rate Application with Higher Specific Energy
journal, August 2009


Electrochemical and Spectroscopic Evidence on the Participation of Quadrivalent Nickel in the Nickel Hydroxide Redox Reaction
journal, January 1989


Characterization of Redox States of Nickel Hydroxide Film Electrodes by In Situ Surface Raman Spectroscopy
journal, January 1988


In situ extended x‐ray absorption fine structure spectroscopy of thin‐film nickel hydroxide electrodes
journal, February 1991


Dynamic EXAFS study of discharging nickel hydroxide electrode with non-integer Ni valency
journal, July 2001


X-Ray Absorption Fine Structure Spectra and the Oxidation State of Nickel in Some of Its Oxycompounds
journal, January 1994


In Situ X-Ray Absorption Near-Edge Structure Evidence for Quadrivalent Nickel in Nickel Battery Electrodes
journal, January 1996


Quantitative Interpretation of K-Edge NEXAFS Data for Various Nickel Hydroxides and the Charged Nickel Electrode
journal, November 1997


Electronic State of Nickel in Barium Nickel Oxide, BaNiO 3
journal, April 1998


Non-cooperative Jahn-Teller effect in LiNiO2: An EXAFS study
journal, April 1995


Ab initio study of lithium intercalation in metal oxides and metal dichalcogenides
journal, July 1997


Electronic structure of Li-doped NiO
journal, January 1992


Various aspects of LiNiO 2 chemistry: A review
journal, January 2005


X-ray photoelectron spectroscopic chemical state quantification of mixed nickel metal, oxide and hydroxide systems
journal, April 2009


New interpretations of XPS spectra of nickel metal and oxides
journal, May 2006


Voltammetric and XPS investigations of nickel hydroxide electrochemically dispersed on gold surface electrodes
journal, February 1999


Dissolution and passivation of nickel. An X-ray photoelectron spectroscopic study
journal, January 1977

  • Dickinson, Thomas; Povey, Andrew F.; Sherwood, Peter M. A.
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 73, Issue 0
  • https://doi.org/10.1039/f19777300327

Electronic Structure of Lithium Nickel Oxides by Electron Energy Loss Spectroscopy
journal, June 2005


Changes in Chemical Bondings by Li Deintercalation in LiMO 2 (M=Cr, V, Co and Ni)
journal, April 1999


Changes in electronic structure by Li ion deintercalation in LiNiO2 from nickel L-edge and O K-edge XANES
journal, July 2001


White lines and d -band occupancy for the 3 d transition-metal oxides and lithium transition-metal oxides
journal, June 2004


Character of Holes in Li x Ni 1 x O and Their Magnetic Behavior
journal, January 1989


Orbital Frustration at the Origin of the Magnetic Behavior in LiNiO 2
journal, April 2001


Surface properties of LiCoO2, LiNiO2 and LiNi1−xCoxO2
journal, March 2007


Charge disproportionation and Jahn-Teller distortion in LiNiO 2 and NaNiO 2 : A density functional theory study
journal, August 2011


The mechanism of electrodeposition and operation of Ni(OH)2 layers
journal, July 1996


Nickel hydroxide electrodeposition from nickel nitrate solutions: mechanistic studies
journal, February 2001


The Effect of Current and Nickel Nitrate Concentration on the Deposition of Nickel Hydroxide Films
journal, April 1995


Effect of Ions on the Structure of Water: Structure Making and Breaking
journal, March 2009


Electrochemical precipitation of nickel hydroxide
journal, November 2002


Efficient electrochromic nickel oxide thin films by electrodeposition
journal, January 2010


Synthesis and Electrochemical Investigations of Ni[sub 1−x]O Thin Films and Ni[sub 1−x]O on Three-Dimensional Carbon Substrates for Electrochemical Capacitors
journal, January 2005


Metal Oxide Catalysts for the Evolution of O 2 from H 2 O
journal, March 2008


Three-dimensional bicontinuous ultrafast-charge and -discharge bulk battery electrodes
journal, March 2011


Ni(OH) 2 Nanoplates Grown on Graphene as Advanced Electrochemical Pseudocapacitor Materials
journal, June 2010


X-ray diffraction and micro-Raman spectroscopy analysis of new nickel hydroxide obtained by electrodialysis
journal, April 2000


In Situ Laser Raman Spectroscopic Study of Anodic Corrosion Films on Nickel and Cobalt
journal, January 1984


In situ Raman Spectroscopy Study of the Nickel Oxyhydroxide Electrode (NOE) System
journal, January 1990


Review of the structure and the electrochemistry of nickel hydroxides and oxy-hydroxides
journal, January 1982


Angle-resolved infrared spectroelectrochemistry. 1. An in situ study of thin-film nickel oxide electrodes
journal, January 1989


Extended x-ray absorption fine structure investigations of nickel hydroxides
journal, January 1990


Electrochemical and In Situ Raman Spectroscopic Characterization of Nickel Hydroxide Electrodes
journal, January 1997


Structural models for nickel electrode active mass
journal, March 1988


In Situ Raman Study of Nickel Oxide and Gold-Supported Nickel Oxide Catalysts for the Electrochemical Evolution of Oxygen
journal, April 2012


Photoelectrochemistry of Nickel Hydroxide Thin Films
journal, January 1989


Redox behavior of the nickel oxide electrode system: quartz crystal microbalance studies
journal, January 1997


Osmotic Coefficients and Mean Activity Coefficients of Uni‐univalent Electrolytes in Water at 25°C
journal, October 1972


Proton Intercalation Hysteresis in Charging and Discharging Nickel Hydroxide Electrodes
journal, August 1999


In situ time-resolved x-ray absorption near edge structure study of the nickel oxide electrode
journal, August 1989


Preparation of hexagonal nanoporous nickel hydroxide film and its application for electrochemical capacitor
journal, May 2007


Works referencing / citing this record:

NiFe-Based (Oxy)hydroxide Catalysts for Oxygen Evolution Reaction in Non-Acidic Electrolytes
journal, July 2016


Enhancement of Oxygen Evolution Activity of Nickel Oxyhydroxide by Electrolyte Alkali Cations
journal, July 2019


Oxygen Isotope Labeling Experiments Reveal Different Reaction Sites for the Oxygen Evolution Reaction on Nickel and Nickel Iron Oxides
journal, July 2019


Enhancement of Oxygen Evolution Activity of Nickel Oxyhydroxide by Electrolyte Alkali Cations
journal, July 2019


Spectroelectrochemical study of water oxidation on nickel and iron oxyhydroxide electrocatalysts
journal, November 2019


Monitoring compositional changes in Ni(OH) 2 electrocatalysts employed in the oxygen evolution reaction
journal, January 2019


A nanostructured nickel/carbon matrix as an efficient oxygen evolution reaction electrocatalyst for rechargeable zinc–air batteries
journal, January 2019


Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films
journal, January 2017


Characterization of NiFe oxyhydroxide electrocatalysts by integrated electronic structure calculations and spectroelectrochemistry
journal, March 2017