Structure-mechanical properties correlation in bulk LiPON glass produced by nitridation of metaphosphate melts

Torres, Victor M.; Kalnaus, Sergiy; Martin, Steve W.; Duggan, Caitlin; Westover, Andrew S.

doi:10.1111/jace.19327

Structure-mechanical properties correlation in bulk LiPON glass produced by nitridation of metaphosphate melts

Journal Article · Fri Jul 14 00:00:00 EDT 2023 · Journal of the American Ceramic Society

DOI:https://doi.org/10.1111/jace.19327· OSTI ID:1991729

Torres, Victor M. ^[1]; ^[2]; ^[1]; Duggan, Caitlin ^[3]; ^[4]

Iowa State Univ., Ames, IA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Computational Sciences and Engineering Division
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

The glassy solid electrolyte Lithium phosphorous oxynitride (LiPON) has been widely researched in thin film solid state battery format due to its outstanding stability when cycled against lithium. In addition, recent reports show thin film LiPON having interesting mechanical behaviors, especially its ability to resist micro-scale cracking via densification and shear flow. Here, in the present study, we have produced bulk LiPON glasses with varying nitrogen contents by ammonolysis of LiPO₃ melts. The resulting compositions were determined to be LiPO_3-3z/2N_z, where 0 ≤ z ≤ 0.75, and the z value of 0.75 is among the highest ever reported for this series of LiPON glasses. The short-range order structures of the different resulting compositions were characterized by infrared, Raman, ³¹P magic angle spinning nuclear magnetic resonance, and X-ray photoelectron spectroscopies. Instrumented nano-indentation was used to measure mechanical properties. It was observed that similar to previous studies, both trigonally coordinated (N_t) and doubly bonded (N_d) N co-exist in the glasses in about the same amounts for z ≤ 0.36, the limit of N content in most previous studies. For glasses with z > 0.36, it was found that the fraction of the N_t increased significantly while the fraction of N_d correspondingly decreased. The incorporation of nitrogen increased both the elastic modulus and hardness of the glass by approximately a factor of 1.5 when N/P ratio reaches 0.75. At the same time, an apparent embrittlement of the glass was observed due to nitridation, which was revealed by nanoindentation with an extra sharp nanoindenter tip.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO); USDOE Advanced Research Projects Agency - Energy (ARPA-E); National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; EE0008852; AR0000654; AR0000778

OSTI ID:: 1991729

Alternate ID(s):: OSTI ID: 1995302

Journal Information:: Journal of the American Ceramic Society, Journal Name: Journal of the American Ceramic Society Journal Issue: 11 Vol. 106; ISSN 0002-7820

Publisher:: American Ceramic SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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