Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab Initio Approach
Abstract
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.
- Authors:
-
[1];
[2];
[2];
[2];
[1];
[2]
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Univ. of California, San Diego, La Jolla, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Univ. of California, San Diego, La Jolla, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation Major Research Instrumentation Program; National Science Foundation (NSF)
- OSTI Identifier:
- 1708990
- Alternate Identifier(s):
- OSTI ID: 1706486; OSTI ID: 1786043
- Report Number(s):
- LLNL-JRNL-810272
Journal ID: ISSN 1433-7851; 1016809
- Grant/Contract Number:
- AC52-07NA27344; SC0002357; CHE‐1338173; ACI‐1548562
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 59; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ab initio calculations; GIPAW; LiPON; solid electrolytes; solid-state NMR spectroscopy
Citation Formats
Marple, Maxwell A. T., Wynn, Thomas A., Cheng, Diyi, Shimizu, Ryosuke, Mason, Harris E., and Meng, Y. Shirley. Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab Initio Approach. United States: N. p., 2020.
Web. doi:10.1002/anie.202009501.
Marple, Maxwell A. T., Wynn, Thomas A., Cheng, Diyi, Shimizu, Ryosuke, Mason, Harris E., & Meng, Y. Shirley. Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab Initio Approach. United States. https://doi.org/10.1002/anie.202009501
Marple, Maxwell A. T., Wynn, Thomas A., Cheng, Diyi, Shimizu, Ryosuke, Mason, Harris E., and Meng, Y. Shirley. Thu .
"Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab Initio Approach". United States. https://doi.org/10.1002/anie.202009501. https://www.osti.gov/servlets/purl/1708990.
@article{osti_1708990,
title = {Local Structure of Glassy Lithium Phosphorus Oxynitride Thin Films: A Combined Experimental and Ab Initio Approach},
author = {Marple, Maxwell A. T. and Wynn, Thomas A. and Cheng, Diyi and Shimizu, Ryosuke and Mason, Harris E. and Meng, Y. Shirley},
abstractNote = {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.},
doi = {10.1002/anie.202009501},
journal = {Angewandte Chemie (International Edition)},
number = ,
volume = 59,
place = {United States},
year = {Thu Aug 20 00:00:00 EDT 2020},
month = {Thu Aug 20 00:00:00 EDT 2020}
}
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Works referenced in this record:
MATPASS/CPMG: A sensitivity enhanced magic-angle spinning sideband separation experiment for disordered solids
journal, August 2012
- Hung, Ivan; Edwards, Trenton; Sen, Sabyasachi
- Journal of Magnetic Resonance, Vol. 221
Structure of Phosphorus Oxynitride Glasses
journal, September 1987
- Bunker, Bruce C.; Tallant, David R.; Balfe, Carol A.
- Journal of the American Ceramic Society, Vol. 70, Issue 9
Review: the structure of simple phosphate glasses
journal, March 2000
- Brow, Richard K.
- Journal of Non-Crystalline Solids, Vol. 263-264
Solid Electrolyte: the Key for High-Voltage Lithium Batteries
journal, October 2014
- Li, Juchuan; Ma, Cheng; Chi, Miaofang
- Advanced Energy Materials, Vol. 5, Issue 4
Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations
journal, October 2015
- Zhu, Yizhou; He, Xingfeng; Mo, Yifei
- ACS Applied Materials & Interfaces, Vol. 7, Issue 42
Structure of Amorphous Selenium by 2D 77 Se NMR Spectroscopy: An End to the Dilemma of Chain versus Ring
journal, July 2017
- Marple, Maxwell; Badger, Jackson; Hung, Ivan
- Angewandte Chemie, Vol. 129, Issue 33
Perspective: Highly stable vapor-deposited glasses
journal, December 2017
- Ediger, M. D.
- The Journal of Chemical Physics, Vol. 147, Issue 21
Perspective: Supercooled liquids and glasses
journal, August 2012
- Ediger, M. D.; Harrowell, Peter
- The Journal of Chemical Physics, Vol. 137, Issue 8
Understanding Glass through Differential Scanning Calorimetry
journal, May 2019
- Zheng, Qiuju; Zhang, Yanfei; Montazerian, Maziar
- Chemical Reviews, Vol. 119, Issue 13
Designing solid-state electrolytes for safe, energy-dense batteries
journal, February 2020
- Zhao, Qing; Stalin, Sanjuna; Zhao, Chen-Zi
- Nature Reviews Materials, Vol. 5, Issue 3
NMR studies of oxide-based glasses
journal, January 2012
- Edén, Mattias
- Annual Reports Section "C" (Physical Chemistry), Vol. 108
31P MAS NMR and DFT study of crystalline phosphate matrices
journal, February 2020
- Martel, Laura; Kovács, Attila; Popa, Karin
- Solid State Nuclear Magnetic Resonance, Vol. 105
Measurements of chain length distributions in calcium phosphate glasses using 2D double quantum NMR
journal, December 1998
- Witter, R.; Hartmann, P.; Vogel, J.
- Solid State Nuclear Magnetic Resonance, Vol. 13, Issue 3
Organic Glasses with Exceptional Thermodynamic and Kinetic Stability
journal, January 2007
- Swallen, S. F.; Kearns, K. L.; Mapes, M. K.
- Science, Vol. 315, Issue 5810
Structural absorption by barbule microstructures of super black bird of paradise feathers
journal, January 2018
- McCoy, Dakota E.; Feo, Teresa; Harvey, Todd Alan
- Nature Communications, Vol. 9, Issue 1
Kinetics‐Controlled Degradation Reactions at Crystalline LiPON/Li x CoO 2 and Crystalline LiPON/Li‐Metal Interfaces
journal, March 2018
- Leung, Kevin; Pearse, Alexander J.; Talin, A. Alec
- ChemSusChem, Vol. 11, Issue 12
Nitridation of alkali metaphosphate glasses: a comparative structural analysis of the Na–P–O–N and Li–Na–P–O–N systems
journal, November 2001
- Le Sauze, André; Montagne, Lionel; Palavit, Gérard
- Journal of Non-Crystalline Solids, Vol. 293-295
All-electron magnetic response with pseudopotentials: NMR chemical shifts
journal, May 2001
- Pickard, Chris J.; Mauri, Francesco
- Physical Review B, Vol. 63, Issue 24
Mechanical characterization of LiPON films using nanoindentation
journal, October 2011
- Herbert, E. G.; Tenhaeff, W. E.; Dudney, N. J.
- Thin Solid Films, Vol. 520, Issue 1
Interface reactions between LiPON and lithium studied by in-situ X-ray photoemission
journal, May 2015
- Schwöbel, André; Hausbrand, René; Jaegermann, Wolfram
- Solid State Ionics, Vol. 273
New insights into the structure of oxynitride NaPON phosphate glasses by 17-oxygen NMR
journal, March 2013
- Muñoz, F.; Delevoye, L.; Montagne, L.
- Journal of Non-Crystalline Solids, Vol. 363
Part 1. 125Te NMR study of tellurite crystals
journal, January 1999
- Sakida, Shinichi; Hayakawa, Satoshi; Yoko, Toshinobu
- Journal of Non-Crystalline Solids, Vol. 243, Issue 1
Possible Existence of a Monovalent Coordination for Nitrogen Atoms in Li x PO y N z Solid Electrolyte: Modeling of X-ray Photoelectron Spectroscopy and Raman Spectra
journal, October 2015
- Guille, Émilie; Vallverdu, Germain; Tison, Yann
- The Journal of Physical Chemistry C, Vol. 119, Issue 41
Dense Glass Packing Can Slow Reactions with an Atmospheric Gas
journal, October 2019
- Qiu, Yue; Bieser, Michael E.; Ediger, M. D.
- The Journal of Physical Chemistry B, Vol. 123, Issue 47
Increased electrical conductivity of LiPON glasses produced by ammonolysis
journal, June 2008
- Munoz, F.; Duran, A.; Pascual, L.
- Solid State Ionics, Vol. 179, Issue 15-16
Influence of radio frequency power on structure and ionic conductivity of LiPON thin films
journal, August 2008
- Hu, Zongqian; Li, Dezhan; Xie, Kai
- Bulletin of Materials Science, Vol. 31, Issue 4
Interfacial instability of amorphous LiPON against lithium: A combined Density Functional Theory and spectroscopic study
journal, June 2017
- Sicolo, Sabrina; Fingerle, Mathias; Hausbrand, René
- Journal of Power Sources, Vol. 354
Structure of Amorphous Selenium by 2D 77 Se NMR Spectroscopy: An End to the Dilemma of Chain versus Ring
journal, August 2017
- Marple, Maxwell; Badger, Jackson; Hung, Ivan
- Angewandte Chemie International Edition, Vol. 56, Issue 33
Ab initio computation for solid-state 31 P NMR of inorganic phosphates: revisiting X-ray structures
journal, January 2019
- Pilar, Kartik; Deng, Zeyu; Preefer, Molleigh B.
- Physical Chemistry Chemical Physics, Vol. 21, Issue 19
Local structure and connectivity in lithium phosphate glasses: a solid-state 31P MAS NMR and 2D exchange investigation
journal, January 1998
- Alam, Todd M.; Brow, Richard K.
- Journal of Non-Crystalline Solids, Vol. 223, Issue 1-2
Electrodiffusion versus Chemical Diffusion in Alkali Calcium Phosphate Glasses: Implication of Structural Changes
journal, February 2017
- Hein, Anneli; Martin, Johannes; Schäfer, Martin
- The Journal of Physical Chemistry C, Vol. 121, Issue 6
Atomic-scale origin of the large grain-boundary resistance in perovskite Li-ion-conducting solid electrolytes
journal, January 2014
- Ma, Cheng; Chen, Kai; Liang, Chengdu
- Energy & Environmental Science, Vol. 7, Issue 5
High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes
journal, January 2019
- Han, Fudong; Westover, Andrew S.; Yue, Jie
- Nature Energy, Vol. 4, Issue 3
Two New, Metastable Polymorphs of Lithium Pyrophosphate Li 4 P 2 O 7: Two New, Metastable Polymorphs of Lithium Pyrophosphate Li 4 P 2 O 7
journal, December 2018
- Raguž, Branimir; Wittich, Knut; Glaum, Robert
- European Journal of Inorganic Chemistry, Vol. 2019, Issue 11-12
Phosphorus oxynitride glasses
journal, February 1995
- Reidmeyer, Mary R.; Day, Delbert E.
- Journal of Non-Crystalline Solids, Vol. 181, Issue 3
Ultrastable Amorphous Sb 2 Se 3 Film
journal, August 2017
- Zhang, Kai; Li, Yang; Huang, Quan
- The Journal of Physical Chemistry B, Vol. 121, Issue 34
Dielectric properties, conductivity and Li+ ion motion in LiPON thin films
journal, December 2013
- Le Van-Jodin, Lucie; Ducroquet, Frédérique; Sabary, Frédéric
- Solid State Ionics, Vol. 253
Effect of high temperature LiPON electrolyte in all solid state batteries
journal, September 2019
- Sepúlveda, Alfonso; Criscuolo, Francesca; Put, Brecht
- Solid State Ionics, Vol. 337
Synthesis, Crystal Structure, and Ionic Conductivity of a Polycrystalline Lithium Phosphorus Oxynitride with the γ-Li3PO4 Structure
journal, March 1995
- Wang, B.; Chakoumakos, B. C.; Sales, B. C.
- Journal of Solid State Chemistry, Vol. 115, Issue 2
Machine learning enabled autonomous microstructural characterization in 3D samples
journal, January 2020
- Chan, Henry; Cherukara, Mathew; Loeffler, Troy D.
- npj Computational Materials, Vol. 6, Issue 1
Artificial Solid Electrolyte Interphase To Address the Electrochemical Degradation of Silicon Electrodes
journal, June 2014
- Li, Juchuan; Dudney, Nancy J.; Nanda, Jagjit
- ACS Applied Materials & Interfaces, Vol. 6, Issue 13
First-principles calculations on structure and properties of amorphous Li5P4O8N3 (LiPON)
journal, November 2016
- Sicolo, Sabrina; Albe, Karsten
- Journal of Power Sources, Vol. 331
Electrical properties of amorphous lithium electrolyte thin films
journal, July 1992
- Bates, J. B.; Dudney, N. J.; Gruzalski, G. R.
- Solid State Ionics, Vol. 53-56, Issue Part 1, p. 647-654
Comments on the structure of LiPON thin-film solid electrolytes
journal, January 2012
- Muñoz, Francisco
- Journal of Power Sources, Vol. 198
Sputter deposited LiPON thin films from powder target as electrolyte for thin film battery applications
journal, March 2011
- Nimisha, C. S.; Rao, K. Yellareswar; Venkatesh, G.
- Thin Solid Films, Vol. 519, Issue 10
Resolving the Amorphous Structure of Lithium Phosphorus Oxynitride (Lipon)
journal, July 2018
- Lacivita, Valentina; Westover, Andrew S.; Kercher, Andrew
- Journal of the American Chemical Society, Vol. 140, Issue 35
Structural Features of LiPON Glasses Determined by 1D and 2D 31 P MAS NMR
journal, May 2015
- Mascaraque, Nerea; Durán, Alicia; Muñoz, Francisco
- International Journal of Applied Glass Science, Vol. 7, Issue 1
Solid-State NMR Studies of Lithium Phosphorus Oxynitride Films Prepared by Nitrogen Ion Beam-Assisted Deposition
journal, January 2005
- Stallworth, P. E.; Vereda, F.; Greenbaum, S. G.
- Journal of The Electrochemical Society, Vol. 152, Issue 3
Interface Stability in Solid-State Batteries
journal, December 2015
- Richards, William D.; Miara, Lincoln J.; Wang, Yan
- Chemistry of Materials, Vol. 28, Issue 1
Structural and Compositional Factors That Control the Li-Ion Conductivity in LiPON Electrolytes
journal, September 2018
- Lacivita, Valentina; Artrith, Nongnuch; Ceder, Gerbrand
- Chemistry of Materials, Vol. 30, Issue 20
Dendrite Growth in Lithium/Polymer Systems
journal, January 2003
- Monroe, Charles; Newman, John
- Journal of The Electrochemical Society, Vol. 150, Issue 10
Mechanism of Lithium Metal Penetration through Inorganic Solid Electrolytes
journal, July 2017
- Porz, Lukas; Swamy, Tushar; Sheldon, Brian W.
- Advanced Energy Materials, Vol. 7, Issue 20
Probing Solid–Solid Interfacial Reactions in All-Solid-State Sodium-Ion Batteries with First-Principles Calculations
journal, December 2017
- Tang, Hanmei; Deng, Zhi; Lin, Zhuonan
- Chemistry of Materials, Vol. 30, Issue 1