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Title: Resolving the Amorphous Structure of Lithium Phosphorus Oxynitride (Lipon)

Abstract

© 2018 American Chemical Society. Lithium phosphorus oxynitride, also known as Lipon, solid-state electrolytes are at the center of the search for solid-state Li metal batteries. Key to the performance of Lipon is a combination of high Li content, amorphous character, and the incorporation of N into the structure. Despite the material's importance, our work presents the first study to fully resolve the structure of Lipon using a combination of ab initio molecular dynamics, density functional theory, neutron scattering, and infrared spectroscopy. The modeled and experimental results have exceptional agreement in both neutron pair distribution function and infrared spectroscopy. Building on this synergy, the structural models show that N forms both bridges between two phosphate units and nonbridging apical N. We further show that as the Li content is increased the ratio of bridging to apical N shifts from being predominantly bridging at Li contents around 2.5:1 Li:P to only apical N at higher Li contents of 3.38:1 Li:P. This crossover from bridging to apical N appears to directly correlate with and explain both the increase in ionic conductivity with the incorporation of N and the ionic conductivity trends found in the literature.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2];  [3];  [2]; ORCiD logo [2];  [4];  [2]
  1. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
  2. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  3. Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States; The Bredesen Center for Interdisciplinary Research and Graduate Education, University of Tennessee, Knoxville, Tennessee 37996, United States
  4. Materials Sciences 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); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
OSTI Identifier:
1479777
Alternate Identifier(s):
OSTI ID: 1477380
Grant/Contract Number:  
AC02-05CH11231; AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 35; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lacivita, Valentina, Westover, Andrew S., Kercher, Andrew, Phillip, Nathan D., Yang, Guang, Veith, Gabriel, Ceder, Gerbrand, and Dudney, Nancy J. Resolving the Amorphous Structure of Lithium Phosphorus Oxynitride (Lipon). United States: N. p., 2018. Web. doi:10.1021/jacs.8b05192.
Lacivita, Valentina, Westover, Andrew S., Kercher, Andrew, Phillip, Nathan D., Yang, Guang, Veith, Gabriel, Ceder, Gerbrand, & Dudney, Nancy J. Resolving the Amorphous Structure of Lithium Phosphorus Oxynitride (Lipon). United States. doi:10.1021/jacs.8b05192.
Lacivita, Valentina, Westover, Andrew S., Kercher, Andrew, Phillip, Nathan D., Yang, Guang, Veith, Gabriel, Ceder, Gerbrand, and Dudney, Nancy J. Mon . "Resolving the Amorphous Structure of Lithium Phosphorus Oxynitride (Lipon)". United States. doi:10.1021/jacs.8b05192. https://www.osti.gov/servlets/purl/1479777.
@article{osti_1479777,
title = {Resolving the Amorphous Structure of Lithium Phosphorus Oxynitride (Lipon)},
author = {Lacivita, Valentina and Westover, Andrew S. and Kercher, Andrew and Phillip, Nathan D. and Yang, Guang and Veith, Gabriel and Ceder, Gerbrand and Dudney, Nancy J.},
abstractNote = {© 2018 American Chemical Society. Lithium phosphorus oxynitride, also known as Lipon, solid-state electrolytes are at the center of the search for solid-state Li metal batteries. Key to the performance of Lipon is a combination of high Li content, amorphous character, and the incorporation of N into the structure. Despite the material's importance, our work presents the first study to fully resolve the structure of Lipon using a combination of ab initio molecular dynamics, density functional theory, neutron scattering, and infrared spectroscopy. The modeled and experimental results have exceptional agreement in both neutron pair distribution function and infrared spectroscopy. Building on this synergy, the structural models show that N forms both bridges between two phosphate units and nonbridging apical N. We further show that as the Li content is increased the ratio of bridging to apical N shifts from being predominantly bridging at Li contents around 2.5:1 Li:P to only apical N at higher Li contents of 3.38:1 Li:P. This crossover from bridging to apical N appears to directly correlate with and explain both the increase in ionic conductivity with the incorporation of N and the ionic conductivity trends found in the literature.},
doi = {10.1021/jacs.8b05192},
journal = {Journal of the American Chemical Society},
number = 35,
volume = 140,
place = {United States},
year = {2018},
month = {7}
}

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