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Title: Electrochemical Stability of Metastable Materials

Abstract

We present a first-principles-based formalism to provide a quantitative measure of the thermodynamic instability and propensity for electrochemical stabilization, passivation, or corrosion of metastable materials in aqueous media. Here, we demonstrate that this formalism can assess the relative Gibbs free energy of candidate materials in aqueous media as well as their decomposition products, combining solid and aqueous phases, as a function of pH and potential. On the basis of benchmarking against 20 stable as well as metastable materials reported in the literature and also our experimental characterization of metastable triclinic-FeVO 4, we present quantitative estimates for the relative Gibbs free energy and corresponding aqueous regimes where these materials are most likely to be stable, form inert passivating films, or steadily corrode to aqueous species. Furthermore, we show that the structure and composition of the passivating films formed on triclinic-FeVO 4 are also in excellent agreement with the Point Defect Model, as proposed by the corrosion community.

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [2];  [1];  [1]; ORCiD logo [2];  [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1480070
Grant/Contract Number:  
AC02-05CH11231; SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 29; Journal Issue: 23; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Singh, Arunima K., Zhou, Lan, Shinde, Aniketa, Suram, Santosh K., Montoya, Joseph H., Winston, Donald, Gregoire, John M., and Persson, Kristin A. Electrochemical Stability of Metastable Materials. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b03980.
Singh, Arunima K., Zhou, Lan, Shinde, Aniketa, Suram, Santosh K., Montoya, Joseph H., Winston, Donald, Gregoire, John M., & Persson, Kristin A. Electrochemical Stability of Metastable Materials. United States. doi:10.1021/acs.chemmater.7b03980.
Singh, Arunima K., Zhou, Lan, Shinde, Aniketa, Suram, Santosh K., Montoya, Joseph H., Winston, Donald, Gregoire, John M., and Persson, Kristin A. Tue . "Electrochemical Stability of Metastable Materials". United States. doi:10.1021/acs.chemmater.7b03980. https://www.osti.gov/servlets/purl/1480070.
@article{osti_1480070,
title = {Electrochemical Stability of Metastable Materials},
author = {Singh, Arunima K. and Zhou, Lan and Shinde, Aniketa and Suram, Santosh K. and Montoya, Joseph H. and Winston, Donald and Gregoire, John M. and Persson, Kristin A.},
abstractNote = {We present a first-principles-based formalism to provide a quantitative measure of the thermodynamic instability and propensity for electrochemical stabilization, passivation, or corrosion of metastable materials in aqueous media. Here, we demonstrate that this formalism can assess the relative Gibbs free energy of candidate materials in aqueous media as well as their decomposition products, combining solid and aqueous phases, as a function of pH and potential. On the basis of benchmarking against 20 stable as well as metastable materials reported in the literature and also our experimental characterization of metastable triclinic-FeVO4, we present quantitative estimates for the relative Gibbs free energy and corresponding aqueous regimes where these materials are most likely to be stable, form inert passivating films, or steadily corrode to aqueous species. Furthermore, we show that the structure and composition of the passivating films formed on triclinic-FeVO4 are also in excellent agreement with the Point Defect Model, as proposed by the corrosion community.},
doi = {10.1021/acs.chemmater.7b03980},
journal = {Chemistry of Materials},
number = 23,
volume = 29,
place = {United States},
year = {2017},
month = {10}
}

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