Electrochemically induced crystalline-to-amorphization transformation in sodium samarium silicate solid electrolyte for long-lasting sodium metal batteries.

Sun, Ge; Lou, Chenjie; Yi, Boqian; Jia, Wanqing; Wei, Zhixuan; Yao, Shiyu; Lu, Ziheng; Chen, Gang et al. · Nat Commun · 2023

basic_science · Level V

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Abstract

Exploiting solid electrolyte (SE) materials with high ionic conductivity, good interfacial compatibility, and conformal contact with electrodes is essential for solid-state sodium metal batteries (SSBs). Here we report a crystalline Na<sub>5</sub>SmSi<sub>4</sub>O<sub>12</sub> SE which features high room-temperature ionic conductivity of 2.9 × 10<sup>-3</sup> S cm<sup>-1</sup> and a low activation energy of 0.15 eV. All-solid-state symmetric cell with Na<sub>5</sub>SmSi<sub>4</sub>O<sub>12</sub> delivers excellent cycling life over 800 h at 0.15 mA h cm<sup>-2</sup> and a high critical current density of 1.4 mA cm<sup>-2</sup>. Such excellent electrochemical performance is attributed to an electrochemically induced in-situ crystalline-to-amorphous (CTA) transformation propagating from the interface to the bulk during repeated deposition and stripping of sodium, which leads to faster ionic transport and superior interfacial properties. Impressively, the Na|Na<sub>5</sub>SmSi<sub>4</sub>O<sub>12</sub>|Na<sub>3</sub>V<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub> sodium metal batteries achieve a remarkable cycling performance over 4000 cycles (6 months) with no capacity loss. These results not only identify Na<sub>5</sub>SmSi<sub>4</sub>O<sub>12</sub> as a promising SE but also emphasize the potential of the CTA transition as a promising mechanism towards long-lasting SSBs.