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Title: Fluid Structure of Molten LiCl–Li Solutions

Abstract

Molten mixtures of lithium chloride and metallic lithium (LiCl-Li) play an essential role in the electrolytic reduction of various metal oxides. These mixtures possess unique high temperature physical and chemical properties that have been investigated for decades. However, due to their extreme chemical reactivity, no study to date has been capable of definitively proving the basic physical nature of Li dissolution in molten LiCl. In this study, the evolution of the structure of molten LiCl-Li is probed as metallic Li is electrochemically introduced into the melt in situ, using synchrotron radiation experiments based on high energy wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS). The time-resolved scattering results indicate the formation of transient Cl- ion cages surrounding low-density voids with a periodicity of similar to 8.3 angstrom, which suggests the formation of metastable Li nanocluster. The structure of the LiCl-Li nanoclusters in the solution is modeled using ab initio molecular dynamics (AIMD) simulations. We report the simulation results are in agreement with the X-ray diffraction measurement and suggest the nanoclusters are predominantly Li-8, along with smaller clusters.

Authors:
ORCiD logo [1];  [1];  [2];  [1];  [1];  [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC); USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1606536
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 123; Journal Issue: 47; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Lithium chloride; Molten Salt; Pair distribution function; SAXS; WAXS

Citation Formats

Guo, Jicheng, Merwin, Augustus, Benmore, Chris J., Mei, Zhi-Gang, Hoyt, Nathaniel C., and Williamson, Mark A.. Fluid Structure of Molten LiCl–Li Solutions. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.jpcb.9b07479.
Guo, Jicheng, Merwin, Augustus, Benmore, Chris J., Mei, Zhi-Gang, Hoyt, Nathaniel C., & Williamson, Mark A.. Fluid Structure of Molten LiCl–Li Solutions. United States. https://doi.org/10.1021/acs.jpcb.9b07479
Guo, Jicheng, Merwin, Augustus, Benmore, Chris J., Mei, Zhi-Gang, Hoyt, Nathaniel C., and Williamson, Mark A.. Mon . "Fluid Structure of Molten LiCl–Li Solutions". United States. https://doi.org/10.1021/acs.jpcb.9b07479. https://www.osti.gov/servlets/purl/1606536.
@article{osti_1606536,
title = {Fluid Structure of Molten LiCl–Li Solutions},
author = {Guo, Jicheng and Merwin, Augustus and Benmore, Chris J. and Mei, Zhi-Gang and Hoyt, Nathaniel C. and Williamson, Mark A.},
abstractNote = {Molten mixtures of lithium chloride and metallic lithium (LiCl-Li) play an essential role in the electrolytic reduction of various metal oxides. These mixtures possess unique high temperature physical and chemical properties that have been investigated for decades. However, due to their extreme chemical reactivity, no study to date has been capable of definitively proving the basic physical nature of Li dissolution in molten LiCl. In this study, the evolution of the structure of molten LiCl-Li is probed as metallic Li is electrochemically introduced into the melt in situ, using synchrotron radiation experiments based on high energy wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS). The time-resolved scattering results indicate the formation of transient Cl- ion cages surrounding low-density voids with a periodicity of similar to 8.3 angstrom, which suggests the formation of metastable Li nanocluster. The structure of the LiCl-Li nanoclusters in the solution is modeled using ab initio molecular dynamics (AIMD) simulations. We report the simulation results are in agreement with the X-ray diffraction measurement and suggest the nanoclusters are predominantly Li-8, along with smaller clusters.},
doi = {10.1021/acs.jpcb.9b07479},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 47,
volume = 123,
place = {United States},
year = {2019},
month = {11}
}

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