Structural and Compositional Factors That Control the Li-Ion Conductivity in LiPON Electrolytes
Abstract
Amorphous Li-ion conductors are important solid-state electrolytes. However, Li transport in these systems is much less understood than for crystalline materials. We investigate amorphous LiPON electrolytes via ab initio molecular dynamics, providing atomistic-level insight into the mechanisms underlying the Li+ mobility. We find that the latter is strongly influenced by the chemistry and connectivity of phosphate polyanions near Li+. Amorphization generates edge-sharing polyhedral connections between Li(O,N)4 and P(O,N)4, and creates under- and overcoordinated Li sites, which destabilizes the Li+ and enhances their mobility. N substitution for O favors conductivity in two ways: (1) excess Li accompanying 1(N):1(O) substitutions introduces extra carriers; (2) energetically favored N-bridging substitutions condense phosphate units and densify the structure, which, counterintuitively, corresponds to higher Li+ mobility. Finally, bridging N is not only less electronegative than O but also engaged in strong covalent bonds with P. This weakens interactions with neighboring Li+ smoothing the way for their migration. When condensation of PO4 polyhedra leads to the formation of isolated O anions, the Li+ mobility is reduced, highlighting the importance of oxygen partial pressure control during synthesis. Furthermore, this detailed understanding of the structural mechanisms affecting Li+ mobility is the key for optimizing the conductivity of LiPON andmore »
- Authors:
-
[1];
[2];
- Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
- Department of Materials Science and Engineering, University of California, Berkeley, Berkeley, California 94720, United States
- Materials Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, Department of Materials Science and Engineering, University of California, Berkeley, Berkeley, California 94720, United States
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Advanced Research Projects Agency - Energy (ARPA-E)
- OSTI Identifier:
- 1493513
- Alternate Identifier(s):
- OSTI ID: 1492330
- Grant/Contract Number:
- AC02-05-CH11231; AR0000775; AC02-05CH11231
- Resource Type:
- Published Article
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Name: Chemistry of Materials Journal Volume: 30 Journal Issue: 20; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Lacivita, Valentina, Artrith, Nongnuch, and Ceder, Gerbrand. Structural and Compositional Factors That Control the Li-Ion Conductivity in LiPON Electrolytes. United States: N. p., 2018.
Web. doi:10.1021/acs.chemmater.8b02812.
Lacivita, Valentina, Artrith, Nongnuch, & Ceder, Gerbrand. Structural and Compositional Factors That Control the Li-Ion Conductivity in LiPON Electrolytes. United States. https://doi.org/10.1021/acs.chemmater.8b02812
Lacivita, Valentina, Artrith, Nongnuch, and Ceder, Gerbrand. Sat .
"Structural and Compositional Factors That Control the Li-Ion Conductivity in LiPON Electrolytes". United States. https://doi.org/10.1021/acs.chemmater.8b02812.
@article{osti_1493513,
title = {Structural and Compositional Factors That Control the Li-Ion Conductivity in LiPON Electrolytes},
author = {Lacivita, Valentina and Artrith, Nongnuch and Ceder, Gerbrand},
abstractNote = {Amorphous Li-ion conductors are important solid-state electrolytes. However, Li transport in these systems is much less understood than for crystalline materials. We investigate amorphous LiPON electrolytes via ab initio molecular dynamics, providing atomistic-level insight into the mechanisms underlying the Li+ mobility. We find that the latter is strongly influenced by the chemistry and connectivity of phosphate polyanions near Li+. Amorphization generates edge-sharing polyhedral connections between Li(O,N)4 and P(O,N)4, and creates under- and overcoordinated Li sites, which destabilizes the Li+ and enhances their mobility. N substitution for O favors conductivity in two ways: (1) excess Li accompanying 1(N):1(O) substitutions introduces extra carriers; (2) energetically favored N-bridging substitutions condense phosphate units and densify the structure, which, counterintuitively, corresponds to higher Li+ mobility. Finally, bridging N is not only less electronegative than O but also engaged in strong covalent bonds with P. This weakens interactions with neighboring Li+ smoothing the way for their migration. When condensation of PO4 polyhedra leads to the formation of isolated O anions, the Li+ mobility is reduced, highlighting the importance of oxygen partial pressure control during synthesis. Furthermore, this detailed understanding of the structural mechanisms affecting Li+ mobility is the key for optimizing the conductivity of LiPON and other amorphous Li-ion conductors.},
doi = {10.1021/acs.chemmater.8b02812},
journal = {Chemistry of Materials},
number = 20,
volume = 30,
place = {United States},
year = {Sat Sep 15 00:00:00 EDT 2018},
month = {Sat Sep 15 00:00:00 EDT 2018}
}
https://doi.org/10.1021/acs.chemmater.8b02812
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