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Title: Phase Transition and Liquid-like Superionic Conduction in Ag2S

Abstract

Superionic conductivity in certain polymorphs of Ag2S has inspired numerous concepts for materials applications, but the relationship between the structure and the mobility of silver ions remains poorly explored. In this paper, we report ab initio molecular dynamics simulations for low- (acanthite) and high-temperature (argentite) Ag2S polymorphs that reveal the dynamical processes, giving rise to the superionic behavior in the latter. Similarities between their sulfur sublattices enable simulations of silver ion diffusivities and pathways on essentially an equal footing. For the higher temperature polymorph, calculated temperature-dependent mean square displacements and activation energies by the nudged elastic band method show good correspondence with expectations from the experiment. In the superionic state, silver atoms diffuse in a liquid-like behavior with no preferred diffusion pathways, within the relatively stable body-centered cubic sulfur framework. Conversely, conduction in acanthite appears to depend more on the mobilities of electronic charge carriers.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [2]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Univ. Grenoble Alpes, Univ. of Savoie Mont Blanc, CNRS, IRD, IFSTTAR, ISTerre, Grenoble (France)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Univ. Grenoble Alpes, Univ. of Savoie Mont Blanc, CNRS, IRD, IFSTTAR, ISTerre, Grenoble (France)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1639035
Report Number(s):
PNNL-SA-152823
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 124; Journal Issue: 18; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Transport properties; sulfur; diffusion; electrical conductivity; ions

Citation Formats

Simonnin, Pauline, Sassi, Michel, Gilbert, Benjamin, Charlet, Laurent, and Rosso, Kevin M. Phase Transition and Liquid-like Superionic Conduction in Ag2S. United States: N. p., 2020. Web. doi:10.1021/acs.jpcc.0c00260.
Simonnin, Pauline, Sassi, Michel, Gilbert, Benjamin, Charlet, Laurent, & Rosso, Kevin M. Phase Transition and Liquid-like Superionic Conduction in Ag2S. United States. https://doi.org/10.1021/acs.jpcc.0c00260
Simonnin, Pauline, Sassi, Michel, Gilbert, Benjamin, Charlet, Laurent, and Rosso, Kevin M. Tue . "Phase Transition and Liquid-like Superionic Conduction in Ag2S". United States. https://doi.org/10.1021/acs.jpcc.0c00260. https://www.osti.gov/servlets/purl/1639035.
@article{osti_1639035,
title = {Phase Transition and Liquid-like Superionic Conduction in Ag2S},
author = {Simonnin, Pauline and Sassi, Michel and Gilbert, Benjamin and Charlet, Laurent and Rosso, Kevin M.},
abstractNote = {Superionic conductivity in certain polymorphs of Ag2S has inspired numerous concepts for materials applications, but the relationship between the structure and the mobility of silver ions remains poorly explored. In this paper, we report ab initio molecular dynamics simulations for low- (acanthite) and high-temperature (argentite) Ag2S polymorphs that reveal the dynamical processes, giving rise to the superionic behavior in the latter. Similarities between their sulfur sublattices enable simulations of silver ion diffusivities and pathways on essentially an equal footing. For the higher temperature polymorph, calculated temperature-dependent mean square displacements and activation energies by the nudged elastic band method show good correspondence with expectations from the experiment. In the superionic state, silver atoms diffuse in a liquid-like behavior with no preferred diffusion pathways, within the relatively stable body-centered cubic sulfur framework. Conversely, conduction in acanthite appears to depend more on the mobilities of electronic charge carriers.},
doi = {10.1021/acs.jpcc.0c00260},
journal = {Journal of Physical Chemistry. C},
number = 18,
volume = 124,
place = {United States},
year = {2020},
month = {4}
}

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