Mechanically sinterable sulfide Na+ superionic conductors are key to enabling room-temperature-operable all-solid-state Na-ion batteries (ASNBs) for large-scale energy storage applications. To date, few candidates can fulfill the requirement of a high ionic conductivity of ≥1 mS cm-1 using abundant, cost-effective, and nontoxic elements. Herein, the development of a new Na+ superionic conductor, Ca-doped cubic Na3PS4, showing a maximum conductivity of ∼1 mS cm-1 at 25 °C is described. Complementary analyses using conductivity measurement by the AC impedance method, 23Na nuclear magnetic resonance spectroscopy, and density functional theory calculations reveal that the aliovalent substitution of Na+ in Na3PS4 with Ca2+ renders a cubic phase with Na vacancies, which increases the activation barriers but drastically enhances Na-ion diffusion. It is demonstrated that TiS2/Na-Sn ASNBs employing Ca-doped Na3PS4 exhibit a high charge capacity of 200 mA h g-1 at 0.06C, good cycling performance, and higher rate capability than those employing undoped cubic Na3PS4.
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© Copyright 2018 American Chemical Society.
All Science Journal Classification (ASJC) codes
- Chemistry (miscellaneous)
- Renewable Energy, Sustainability and the Environment
- Fuel Technology
- Energy Engineering and Power Technology
- Materials Chemistry