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Title: Hydrogen weakens interlayer bonding in layered transition metal sulfide Fe 1+x S

Abstract

The presence of interlaminar interstitial defects like hydrogen affects the mechanical properties of van der Waals-bonded layered materials such as transition metal chalcogenides. While the embrittling effect of hydrogen is well understood in metals, the impact of hydrogen defects on the mechanical behavior of layered chalcogenides remained unexplored. In this article, we use density functional calculations to reveal the influence of different hydrogen point defects on important mechanical metrics, including binding energies, elastic moduli and tensile and shear strengths of a prototypical ionic layered material, mackinawite, Fe1+xS. We find that one of the low-energy hydrogen defect structures, interlaminar molecular H2 interstitials, severely degrades the strength of inter-layer van der Waals interactions in the mackinawite crystal. This leads to a significant (over 80%) degradation in the mechanical properties of the mackinawite crystal and enables facile interlayer sliding and exfoliation. This finding suggests the mechanisms for cathodic exfoliation of transition metal chalcogenides like Fe1+xS, and presents a plausible mechanism for the poor protectiveness of layered passive films like mackinawite that undergo failure by spalling or delamination.

Authors:
ORCiD logo [1];  [2];  [1]
  1. Laboratory for Electrochemical Interfaces; Massachusetts Institute of Technology; Cambridge; USA; Department of Materials Science and Engineering
  2. Laboratory for Electrochemical Interfaces; Massachusetts Institute of Technology; Cambridge; USA; Department of Nuclear Science and Engineering
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1492297
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Journal of Materials Chemistry A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 10; Journal ID: ISSN 2050-7488
Country of Publication:
United States
Language:
English

Citation Formats

Krishnamoorthy, Aravind, Dinh, Minh A., and Yildiz, Bilge. Hydrogen weakens interlayer bonding in layered transition metal sulfide Fe 1+x S. United States: N. p., 2017. Web. doi:10.1039/c6ta10538f.
Krishnamoorthy, Aravind, Dinh, Minh A., & Yildiz, Bilge. Hydrogen weakens interlayer bonding in layered transition metal sulfide Fe 1+x S. United States. doi:10.1039/c6ta10538f.
Krishnamoorthy, Aravind, Dinh, Minh A., and Yildiz, Bilge. Sun . "Hydrogen weakens interlayer bonding in layered transition metal sulfide Fe 1+x S". United States. doi:10.1039/c6ta10538f.
@article{osti_1492297,
title = {Hydrogen weakens interlayer bonding in layered transition metal sulfide Fe 1+x S},
author = {Krishnamoorthy, Aravind and Dinh, Minh A. and Yildiz, Bilge},
abstractNote = {The presence of interlaminar interstitial defects like hydrogen affects the mechanical properties of van der Waals-bonded layered materials such as transition metal chalcogenides. While the embrittling effect of hydrogen is well understood in metals, the impact of hydrogen defects on the mechanical behavior of layered chalcogenides remained unexplored. In this article, we use density functional calculations to reveal the influence of different hydrogen point defects on important mechanical metrics, including binding energies, elastic moduli and tensile and shear strengths of a prototypical ionic layered material, mackinawite, Fe1+xS. We find that one of the low-energy hydrogen defect structures, interlaminar molecular H2 interstitials, severely degrades the strength of inter-layer van der Waals interactions in the mackinawite crystal. This leads to a significant (over 80%) degradation in the mechanical properties of the mackinawite crystal and enables facile interlayer sliding and exfoliation. This finding suggests the mechanisms for cathodic exfoliation of transition metal chalcogenides like Fe1+xS, and presents a plausible mechanism for the poor protectiveness of layered passive films like mackinawite that undergo failure by spalling or delamination.},
doi = {10.1039/c6ta10538f},
journal = {Journal of Materials Chemistry A},
issn = {2050-7488},
number = 10,
volume = 5,
place = {United States},
year = {2017},
month = {1}
}

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