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Structural Disorder in Li6PS5I Speeds 7Li Nuclear Spin Recovery and Slows Down 31P Relaxation-Implications for Translational and Rotational Jumps as Seen by Nuclear Magnetic Resonance.

ABSTRACT: Lithium-thiophosphates have attracted great attention as they offer a rich playground to develop tailor-made solid electrolytes for clean energy storage systems. Here, we used poorly conducting Li6PS5I, which can be converted into a fast ion conductor by high-energy ball-milling to understand the fundamental guidelines that enable the Li+ ions to quickly diffuse through a polarizable but distorted matrix. In stark contrast to well-crystalline Li6PS5I (10-6 S cm-1), the ionic conductivity of its defect-rich nanostructured analog touches almost the mS cm-1 regime. Most likely, this immense enhancement originates from site disorder and polyhedral distortions introduced during mechanical treatment. We used the spin probes 7Li and 31P to monitor nuclear spin relaxation that is directly induced by Li+ translational and/or PS4 3- rotational motions. Compared to the ordered form, 7Li spin-lattice relaxation (SLR) in nano-Li6PS5I reveals an additional ultrafast process that is governed by activation energy as low as 160 meV. Presumably, this new relaxation peak, appearing at T max = 281 K, reflects extremely rapid Li hopping processes with a jump rate in the order of 109 s-1 at T max. Thus, the thiophosphate transforms from a poor electrolyte with island-like local diffusivity to a fast ion conductor with 3D cross-linked diffusion routes enabling long-range transport. On the other hand, the original 31P nuclear magnetic resonance (NMR) SLR rate peak, pointing to an effective 31P-31P spin relaxation source in ordered Li6PS5I, is either absent for the distorted form or shifts toward much higher temperatures. Assuming the 31P NMR peak as being a result of PS4 3- rotational jump processes, NMR unveils that disorder significantly slows down anion dynamics. The latter finding might also have broader implications and sheds light on the vital question how rotational dynamics are to be manipulated to effectively enhance Li+ cation transport.

SUBMITTER: Brinek M

PROVIDER: S-EPMC7662756 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature

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Structural Disorder in Li6PS5I Speeds 7Li Nuclear Spin Recovery and Slows Down 31P Relaxation-Implications for Translational and Rotational Jumps as Seen by Nuclear Magnetic Resonance.

Brinek M M Hiebl C C Hogrefe K K Hanghofer I I Wilkening H M R HMR

The journal of physical chemistry. C, Nanomaterials and interfaces 20200929 42

Lithium-thiophosphates have attracted great attention as they offer a rich playground to develop tailor-made solid electrolytes for clean energy storage systems. Here, we used poorly conducting Li6PS5I, which can be converted into a fast ion conductor by high-energy ball-milling to understand the fundamental guidelines that enable the Li+ ions to quickly diffuse through a polarizable but distorted matrix. In stark contrast to well-crystalline Li6PS<sub ...[more]

PMID: 33193940

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Project description:The rational development of fast-ion-conducting solid electrolytes for all-solid-state lithium-ion batteries requires understanding the key structural and chemical principles that give some materials their exceptional ionic conductivities. For the lithium argyrodites Li6PS5X (X = Cl, Br, or I), the choice of the halide, X, strongly affects the ionic conductivity, giving room-temperature ionic conductivities for X = {Cl,Br} that are ×103 higher than for X = I. This variation has been attributed to differing degrees of S/X anion disorder. For X = {Cl,Br}, the S/X anions are substitutionally disordered, while for X = I, the anion substructure is fully ordered. To better understand the role of substitutional anion disorder in enabling fast lithium-ion transport, we have performed a first-principles molecular dynamics study of Li6PS5I and Li6PS5Cl with varying amounts of S/X anion-site disorder. By considering the S/X anions as a tetrahedrally close-packed substructure, we identify three partially occupied lithium sites that define a contiguous three-dimensional network of face-sharing tetrahedra. The active lithium-ion diffusion pathways within this network are found to depend on the S/X anion configuration. For anion-disordered systems, the active site-site pathways give a percolating three-dimensional diffusion network; whereas for anion-ordered systems, critical site-site pathways are inactive, giving a disconnected diffusion network with lithium motion restricted to local orbits around S positions. Analysis of the lithium substructure and dynamics in terms of the lithium coordination around each sulfur site highlights a mechanistic link between substitutional anion disorder and lithium disorder. In anion-ordered systems, the lithium ions are pseudo-ordered, with preferential 6-fold coordination of sulfur sites. Long-ranged lithium diffusion would disrupt this SLi6 pseudo-ordering, and is, therefore, disfavored. In anion-disordered systems, the pseudo-ordered 6-fold S-Li coordination is frustrated because of Li-Li Coulombic repulsion. Lithium positions become disordered, giving a range of S-Li coordination environments. Long-ranged lithium diffusion is now possible with no net change in S-Li coordination numbers. This gives rise to superionic lithium transport in the anion-disordered systems, effected by a concerted string-like diffusion mechanism.

Dataset Information

Structural Disorder in Li6PS5I Speeds 7Li Nuclear Spin Recovery and Slows Down 31P Relaxation-Implications for Translational and Rotational Jumps as Seen by Nuclear Magnetic Resonance.

Publications

Structural Disorder in Li<sub>6</sub>PS<sub>5</sub>I Speeds <sup>7</sup>Li Nuclear Spin Recovery and Slows Down <sup>31</sup>P Relaxation-Implications for Translational and Rotational Jumps as Seen by Nuclear Magnetic Resonance.

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