Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab Initio Approach

Marple, Maxwell T.; Wynn, Thomas A.; Cheng, Diyi; Shimizu, Ryosuke; Mason, Harris E.; Meng, Y. Shirley

doi:10.1002/anie.202009501

Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab Initio Approach

Journal Article · Tue Sep 29 00:00:00 EDT 2020 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202009501· OSTI ID:1706486

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Physical and Life Science Directorate Lawrence Livermore National Laboratory Livermore CA 94550 USA; University of California San Diego, CA (United States)
Department Department of NanoEngineering University of California San Diego La Jolla CA 92093 USA
Materials Science & Engineering Program University of California San Diego La Jolla CA 92093 USA
Physical and Life Science Directorate Lawrence Livermore National Laboratory Livermore CA 94550 USA
Department Department of NanoEngineering University of California San Diego La Jolla CA 92093 USA; Materials Science & Engineering Program University of California San Diego La Jolla CA 92093 USA; Sustainable Power and Energy Center University of California San Diego La Jolla CA 92093 USA

Lithium phosphorus oxynitride (LiPON) is an amorphous solid–state lithium ion conductor displaying exemplary cyclability against lithium metal anodes. There is no definitive explanation for this stability due to the limited understanding of the structure of LiPON. Herein, we provide a structural model of RF–sputtered LiPON. Information about the short–range structure results from 1D and 2D solid–state NMR experiments. These results are compared with first principles chemical shielding calculations of Li–P–O/N crystals and ab initio molecular dynamics–generated amorphous LiPON models to unequivocally identify the glassy structure as primarily isolated phosphate monomers with N incorporated in both apical and as bridging sites in phosphate dimers. Structural results suggest LiPON's stability is a result of its glassy character. In conclusion, free–standing LiPON films are produced that exhibit a high degree of flexibility, highlighting the unique mechanical properties of glassy materials.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Univ. of California, San Diego, La Jolla, CA (United States)

Sponsoring Organization:: National Science Foundation; National Science Foundation Major Research Instrumentation Program; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC52-07NA27344; SC0002357

OSTI ID:: 1706486

Alternate ID(s):: OSTI ID: 1708990
OSTI ID: 1786043
OSTI ID: 22972106

Report Number(s):: LLNL-JRNL-810272

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Vol. 59; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab Initio Approach

Journal Article · Mon Sep 28 20:00:00 EDT 2020 · Angewandte Chemie · OSTI ID:1668452

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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solid-state NMR spectroscopy

Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab Initio Approach

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