Abstract The preparation of 0.58 Li2S + 0.315 SiS2+ 0.105 LiPO3glass, and the impacts of polysulfide and P1Pdefect structure impurities on the glass transition temperature (Tg), crystallization temperature (Tc), working range (ΔT≡ Tc‐ Tg), fragility index, and the Raman spectra were evaluated using statistical analysis. In this study, 33 samples of this glass composition were synthesized through melt‐quenching. Thermal analysis was conducted to determine the glass transition temperature, crystallization temperature, working range, and fragility index through differential scanning calorimetry. The quantity of the impurities described above was determined through Raman spectroscopy peak analysis. Elemental sulfur was doped into a glass to quantify the wt% sulfur content in the glasses. Linear regression analysis was conducted to determine the impact of polysulfide impurities and P1Pdefect impurities on the thermal properties. Polysulfide impurities were found to decrease theTgat rate of nearly 12°C per 1 wt% increase in sulfur concentration. The sulfur concentration does not have a statistically significant impact on the other properties (α = 0.05). The P1Pdefect structure appears to decrease the resistance to crystallization of the glass by measurably decreasing the working range of the glasses, but further study is necessary to fully quantify and determine this.
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Structure‐mechanical properties correlation in bulk LiPON glass produced by nitridation of metaphosphate melts
Abstract 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. In the present study, we have produced bulk LiPON glasses with varying nitrogen contents by ammonolysis of LiPO3melts. The resulting compositions were determined to be LiPO3‐3z/2Nz, 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 (Nt) and doubly bonded (Nd) N co‐exist in the glasses in about the same amounts forz ≤ 0.36, the limit of N content in most previous studies. For glasses withz > 0.36, it was found that the fraction of the Ntincreased significantly while the fraction of Ndcorrespondingly 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.
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- Award ID(s):
- 1936913
- PAR ID:
- 10480287
- Publisher / Repository:
- American Ceramic Society
- Date Published:
- Journal Name:
- Journal of the American Ceramic Society
- Volume:
- 106
- Issue:
- 11
- ISSN:
- 0002-7820
- Page Range / eLocation ID:
- 6565 to 6576
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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