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.T here is no definitive explanation for this stability due to the limited understanding of the structure of LiPON.H erein, we provide astructural model of RF-sputtered LiPON.Information about the short-range structure results from 1D and 2D solid-state NMR experiments.T hese results are compared with first principles chemical shielding calculations of LiP -O/N crystals and ab initio molecular dynamics-generated amorphous LiP-ON models to unequivocally identify the glassy structure as primarily isolated phosphate monomers with Ni ncorporated in both apical and as bridging sites in phosphate dimers. Structural results suggest LiPON'ss tability is ar esult of its glassy character.Free-standing LiPON films are produced that exhibit ah igh degree of flexibility,h ighlighting the unique mechanical properties of glassy materials.

Investigating dry room compatibility of sulfide solid-state electrolytes for scalable manufacturing

“…A significant amount of Li 3 PO 4 ( δ iso = 9.3 ppm (ref. 45 and 46)) is formed after heat treatment from both air and water exposed samples, in agreement with XRD and FTIR results. Due to the extreme sulfur loss in the water exposed sample, more sulfur deficient phases are formed (Fig.…”

“…7 Li within phosphorous oxide environments have chemical shis between 1 to 0.14 ppm, so a slight shielding indicates the presence of more oxygen in the Li coordination sphere. 45,46 Aer heat treatment, along with the reformation of LPSCl, the LiCl peak remains along with a prominent shoulder at 2 ppm that is assigned to Li 2 S. 48 The signal for Li 3 PO 4 is not resolvable but is likely contributing to the additional broadening of the peaks between 1-0 ppm. 7 Li spin-lattice relaxation times were measured on all the samples and found largely similar results as obtained by 31 P SLR measurements (Table S3 †).…”

Promising Electrode and Electrolyte Materials for High‐Energy‐Density Thin‐Film Lithium Batteries

“…[112] The ionic conductivity of state-of-the-art LiPON is close to 10 À5 S cm À1 [101] and the studies on structural models and interfacial stability of LiPON have been improved gradually. [102,105,122] It can be predicted that increasing the ionic conductivity and clarifying the structure change could further broaden the application of LiPON film.…”

Solid State NMR Spectroscopy a Valuable Technique for Structural Insights of Advanced Thin Film Materials: A Review

“…Ultra-high magnetic fields resolve to a certain extent the line-broadening associated with the second-order quadrupole coupling [106]. Applying multi-field experiments is a decisive exploration strategy for extracting structural information and exploring the chemical environment of exotic quadrupole nuclei such as 2 H, 17 O, 33 S and 35 Cl in organic thin films and 7 Li, 11 B, 51 V, 59 Co, 67 Zn, 71 Ga and 89 Yb in inorganic ones.…”

“…H [61-64] and 13 C [65-68] nuclei for organic thin films, but extends in inorganic thin films to cover a huge portion from the periodic table such as 2 H [69,70], 7,8 Li [71-73], 11 B [74], 14,15 N [72,75], 17 O [76], 19 F [77-79], 27 Al [80-83], 29 Si [84-87], 31 P [71,72,86,88,89], 55 Mn [90-92], 59 Co [93-95],69,71 Ga[75,96],75 …”