Resolving the Amorphous Structure of Lithium Phosphorus Oxynitride (Lipon)

Lacivita, Valentina; Westover, Andrew S.; Kercher, Andrew K.; Phillip, Nathan D.; Yang, Guang; Veith, Gabriel M.; Ceder, Gerbrand; Dudney, Nancy J.

doi:10.1021/jacs.8b05192

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

Journal Article · Mon Jul 23 00:00:00 EDT 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b05192· OSTI ID:1479777

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Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

© 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.

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Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E)

Grant/Contract Number:: AC05-00OR22725; AC02-05CH11231

OSTI ID:: 1479777

Alternate ID(s):: OSTI ID: 1477380

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 35; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 69 works

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