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Title: Li-ion site disorder driven superionic conductivity in solid electrolytes: a first-principles investigation of β-Li 3PS 4

Abstract

The attractive safety and long-term stability of all solid-state batteries has added a new impetus to the discovery and development of solid electrolytes for lithium batteries. Recently several superionic lithium conducting solid electrolytes have been discovered. All the superionic lithium containing compounds (β-Li 3PS 4 and Li 10GeP 2S 12 and oxides, predominantly in the garnet phase) have partially occupied sites. This naturally begs the question of understanding the role of partial site occupancies (or site disorder) in optimizing ionic conductivity in these family of solids. In this paper, we find that for a given topology of the host lattice, maximizing the number of sites with similar Li-ion adsorption energies, which gives partial site occupancy, is a natural way to increase the configurational entropy of the system and optimize the conductivity. For a given topology and density of Li-ion adsorption sites, the ionic conductivity is maximal when the number of mobile Li-ions are equal to the number of mobile vacancies, also the very condition for achieving maximal configurational entropy. We demonstrate applicability of this principle by elucidating the role of Li-ion site disorder and the local chemical environment in the high ionic conductivity of β-Li 3PS 4. In addition, formore » β-Li 3PS 4 we find that a significant density of vacancies in the Li-ion sub-lattice (~25%) leads to sub-lattice melting at (~600 K) leading to a molten form for the Li-ions in an otherwise solid anionic host. This gives a lithium site occupancy that is similar to what is measured experimentally. We further show that quenching this disorder can improve conductivity at lower temperatures. As a consequence, we discover that (a) one can optimize ionic conductivity in a given topology by choosing a chemistry/composition that maximizes the number of mobile-carriers i.e. maximizing both mobile Li-ions and vacancies, and (b) when the concentration of vacancies becomes significant in the Li-ion sub-lattice, it becomes energetically as well as entropically favorable for it to remain molten well below the bulk decomposition temperature of the solid. Finally, this principle may already apply to several known superionic conducting solids.« less

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC); ORNL Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1408640
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 5; Journal Issue: 3; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Phani Dathar, Gopi Krishna, Balachandran, Janakiraman, Kent, Paul R. C., Rondinone, Adam J., and Ganesh, P. Li-ion site disorder driven superionic conductivity in solid electrolytes: a first-principles investigation of β-Li3PS4. United States: N. p., 2016. Web. doi:10.1039/c6ta07713g.
Phani Dathar, Gopi Krishna, Balachandran, Janakiraman, Kent, Paul R. C., Rondinone, Adam J., & Ganesh, P. Li-ion site disorder driven superionic conductivity in solid electrolytes: a first-principles investigation of β-Li3PS4. United States. doi:10.1039/c6ta07713g.
Phani Dathar, Gopi Krishna, Balachandran, Janakiraman, Kent, Paul R. C., Rondinone, Adam J., and Ganesh, P. Fri . "Li-ion site disorder driven superionic conductivity in solid electrolytes: a first-principles investigation of β-Li3PS4". United States. doi:10.1039/c6ta07713g. https://www.osti.gov/servlets/purl/1408640.
@article{osti_1408640,
title = {Li-ion site disorder driven superionic conductivity in solid electrolytes: a first-principles investigation of β-Li3PS4},
author = {Phani Dathar, Gopi Krishna and Balachandran, Janakiraman and Kent, Paul R. C. and Rondinone, Adam J. and Ganesh, P.},
abstractNote = {The attractive safety and long-term stability of all solid-state batteries has added a new impetus to the discovery and development of solid electrolytes for lithium batteries. Recently several superionic lithium conducting solid electrolytes have been discovered. All the superionic lithium containing compounds (β-Li3PS4 and Li10GeP2S12 and oxides, predominantly in the garnet phase) have partially occupied sites. This naturally begs the question of understanding the role of partial site occupancies (or site disorder) in optimizing ionic conductivity in these family of solids. In this paper, we find that for a given topology of the host lattice, maximizing the number of sites with similar Li-ion adsorption energies, which gives partial site occupancy, is a natural way to increase the configurational entropy of the system and optimize the conductivity. For a given topology and density of Li-ion adsorption sites, the ionic conductivity is maximal when the number of mobile Li-ions are equal to the number of mobile vacancies, also the very condition for achieving maximal configurational entropy. We demonstrate applicability of this principle by elucidating the role of Li-ion site disorder and the local chemical environment in the high ionic conductivity of β-Li3PS4. In addition, for β-Li3PS4 we find that a significant density of vacancies in the Li-ion sub-lattice (~25%) leads to sub-lattice melting at (~600 K) leading to a molten form for the Li-ions in an otherwise solid anionic host. This gives a lithium site occupancy that is similar to what is measured experimentally. We further show that quenching this disorder can improve conductivity at lower temperatures. As a consequence, we discover that (a) one can optimize ionic conductivity in a given topology by choosing a chemistry/composition that maximizes the number of mobile-carriers i.e. maximizing both mobile Li-ions and vacancies, and (b) when the concentration of vacancies becomes significant in the Li-ion sub-lattice, it becomes energetically as well as entropically favorable for it to remain molten well below the bulk decomposition temperature of the solid. Finally, this principle may already apply to several known superionic conducting solids.},
doi = {10.1039/c6ta07713g},
journal = {Journal of Materials Chemistry. A},
number = 3,
volume = 5,
place = {United States},
year = {2016},
month = {12}
}

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Figures / Tables:

Fig. 1 Fig. 1 : (a) is a schematic showing how to achieve weak/strong disorder in a system with multiple sites for lithium adsorption. Degree of disorder can be modified chemically or by the applications of strain (b) schematic of the energy surface for the number of accessible configurational states with volumemore » W ⇠ NCm where N is the number of available sites and m is the number of free carriers. When the number of accessible states reaches a maximum in 3D, one achieves maximum ionic conductivity.« less

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