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Kinetically Stabilized Cation Arrangement in Li₃ YCl₆ Superionic Conductor during Solid-State Reaction.

ABSTRACT: The main approach for exploring metastable materials is via trial-and-error synthesis, and there is limited understanding of how metastable materials are kinetically stabilized. In this study, a metastable phase superionic conductor, β-Li₃ YCl₆ , is discovered through in situ X-ray diffraction after heating a mixture of LiCl and YCl₃ powders. While Cl^- arrangement is represented as a hexagonal close packed structure in both metastable β-Li₃ YCl₆ synthesized below 600 K and stable α-Li₃ YCl₆ above 600 K, the arrangement of Li⁺ and Y³⁺ in β-Li₃ YCl₆ determined by neutron diffraction brought about the cell with a 1/√3 a-axis and a similar c-axis of stable α-Li₃ YCl₆ . Higher Li⁺ ion conductivity and lower activation energy for Li⁺ transport are observed in comparison with α-Li₃ YCl₆ . The computationally calculated low migration barrier of Li⁺ supports the low activation energy for Li⁺ conduction, and the calculated high migration barrier of Y³⁺ kinetically stabilizes this metastable phase by impeding phase transformation to α-Li₃ YCl₆ . This work shows that the combination of in situ observation of solid-state reactions and computation of the migration energy can facilitate the comprehension of the solid-state reactions allowing kinetic stabilization of metastable materials, and can enable the discovery of new metastable materials in a short time.

SUBMITTER: Ito H

PROVIDER: S-EPMC8336504 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The development of fast Li ion-conducting materials for use as solid electrolytes that provide sufficient electrochemical stability against electrode materials is paramount for the future of all-solid-state batteries. Advances on these fast ionic materials are dependent on building structure-ionic mobility-function relationships. Here, we exploit a series of multinuclear and multidimensional nuclear magnetic resonance (NMR) approaches, including 6Li and 31P magic angle spinning (MAS), in conjunction with density functional theory (DFT) to provide a detailed understanding of the local structure of the ultraphosphate Li3P5O14, a promising candidate for an oxide-based Li ion conductor that has been shown to be a highly conductive, energetically favorable, and electrochemically stable potential solid electrolyte. We have reported a comprehensive assignment of the ultraphosphate layer and layered Li6O16 26- chains through 31P and 6Li MAS NMR, respectively, in conjunction with DFT. The chemical shift anisotropy of the eight resonances with the lowest 31P chemical shift is significantly lower than that of the 12 remaining resonances, suggesting the phosphate bonding nature of these P sites being one that bridges to three other phosphate groups. We employed a number of complementary 6,7Li NMR techniques, including MAS variable-temperature line narrowing spectra, spin-alignment echo (SAE) NMR, and relaxometry, to quantify the lithium ion dynamics in Li3P5O14. Detailed analysis of the diffusion-induced spin-lattice relaxation data allowed for experimental verification of the three-dimensional Li diffusion previously proposed computationally. The 6Li NMR relaxation rates suggest sites Li1 and Li5 (the only five-coordinate Li site) are the most mobile and are adjacent to one another, both in the a-b plane (intralayer) and on the c-axis (interlayer). As shown in the 6Li-6Li exchange spectroscopy NMR spectra, sites Li1 and Li5 likely exchange with one another both between adjacent layered Li6O16 26- chains and through the center of the P12O36 12- rings forming the three-dimensional pathway. The understanding of the Li ion mobility pathways in high-performing solid electrolytes outlines a route for further development of such materials to improve their performance.

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Kinetically Stabilized Cation Arrangement in Li₃ YCl₆ Superionic Conductor during Solid-State Reaction.

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Kinetically Stabilized Cation Arrangement in Li₃ YCl₆ Superionic Conductor during Solid-State Reaction.