Yu, ZhaoxinZhaoxinYuShang, Shun-LiShun-LiShangWang, DaiweiDaiweiWangLi, Yuguang C.Yuguang C.LiYennawar, Hemant P.Hemant P.YennawarLi, GuoxingGuoxingLiHAW-TYNG HUANGGao, YueYueGaoMallouk, Thomas E.Thomas E.MalloukLiu, Zi-KuiZi-KuiLiuWang, DonghaiDonghaiWang2024-09-182024-09-182019https://www.scopus.com/record/display.uri?eid=&origin=resultslisthttps://scholars.lib.ntu.edu.tw/handle/123456789/721229All-solid-state Na-ion batteries (NIBs) that incorporate nonflammable solid-state electrolytes and an inexhaustible alkali metal offer a potential solution to the safety and cost concerns associated with conventional Li-ion batteries that use liquid electrolytes. Na-ion solid-state electrolytes (SSEs) with high ionic conductivity are the key to success for all-solid-state NIBs. Here, we report a new Na-ion SSE, Na11Sn2PSe12, with a superior grain conductivity of 3.04 mS cm−1 and a total ionic conductivity of 2.15 mS cm−1 at 25 °C. Single-crystal X-ray diffraction, first-principles phonon calculations, and the proposed bonding energy model indicate that its superior ionic conductivity stems from the presence of a high density of dispersive Na+ vacancies, three-dimensional Na-ion conduction pathways, and a low bonding energy of the Na+ ion with its neighboring atoms. Na11Sn2PSe12 is used for the first time as the electrolyte in all-solid-state Na-Sn/TiS2 battery cell, which shows excellent rate performance and delivers a high reversible capacity of 66.2 mAh (g of TiS2)−1 after 100 cycles with cycling retention of 88.3% at a rate of 0.1 C at room temperature. © 2018Density functional theorySelenidesSingle crystal X-raySodium-ion batteriesSolid-state electrolytesjournal article10.1016/j.ensm.2018.11.0272-s2.0-85058481107