Dataset Information

Correlating local structure and migration dynamics in Na/Li dual ion conductor Na₅YSi₄O₁₂.

ABSTRACT: Na₅YSi₄O₁₂ (NYSO) is demonstrated as a promising electrolyte with high ionic conductivity and low activation energy for practical use in solid Na-ion batteries. Solid-state NMR was employed to identify the six types of coordination of Na⁺ ions and migration pathway, which is vital to master working mechanism and enhance performance. The assignment of each sodium site is clearly determined from high-quality ²³Na NMR spectra by the aid of Density Functional Theory calculation. Well-resolved ²³Na exchangespectroscopy and electrochemical tracer exchange spectra provide the first experimental evidence to show the existence of ionic exchange between sodium at Na5 and Na6 sites, revealing that Na transport route is possibly along three-dimensional chain of open channel-Na4-open channel. Variable-temperature NMR relaxometry is developed to evaluate Na jump rates and self-diffusion coefficient to probe the sodium-ion dynamics in NYSO. Furthermore, NYSO works well as a dual ion conductor in Na and Li metal batteries with Na₃V₂(PO₄)₃ and LiFePO₄ as cathodes, respectively.

SUBMITTER: Lou C

PROVIDER: S-EPMC11331078 | biostudies-literature | 2024 Aug

REPOSITORIES: biostudies-literature

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Publications

Correlating local structure and migration dynamics in Na/Li dual ion conductor Na5YSi4O12.

Lou Chenjie C Liu Jie J Sun Xuan X Zhang Wenda W Xu Ligang L Luo Huajie H Chen Yongjin Y Gao Xiang X Kuang Xiaojun X Fu Jipeng J Xu Jun J Su Lei L Ma Jiwei J Tang Mingxue M

Proceedings of the National Academy of Sciences of the United States of America 20240808 33

Na5YSi4O12 (NYSO) is demonstrated as a promising electrolyte with high ionic conductivity and low activation energy for practical use in solid Na-ion batteries. Solid-state NMR was employed to identify the six types of coordination of Na+ ions and migration pathway, which is vital to master working mechanism and enhance performance. The assignment of each sodium site is clearly determined from high-quality 23Na NMR spectra by the aid of Dens ...[more]

PMID: 39116136

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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.

Dataset Information

Correlating local structure and migration dynamics in Na/Li dual ion conductor Na₅YSi₄O₁₂.

Publications

Correlating local structure and migration dynamics in Na/Li dual ion conductor Na<sub>5</sub>YSi<sub>4</sub>O<sub>12</sub>.

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