Powder X-ray diffraction XRD (CuK α) patterns of the prepared samples were obtained with a diffractmeter (SmartLab Rigaku). The mixture of the starting materials was poured into a 45 mL zirconia pot with 500 zirconia balls (4 mm in diameter), and mechanically milled at the rotation speed of 380 rpm for 10 hours. a-Na 2TiS 3 was prepared by mechanochemical synthesis from Na 2S and TiS 2. The sealed sample was heated at 500 ☌ for 5 hours and slowly cooled in an electrical furnace. The mixture of the starting materials was placed into a carbon crucible and further sealed in a quartz tube under vacuum. It is revealed that amorphization of Na 2TiS 3 is effective in increasing the reversible capacity.Ĭ-Na 2TiS 3 was synthesized by conventional solid phase reaction with heat treatment of Na 2S (Nagao Co. All-solid-state cells with a-Na 2TiS 3 showed nearly twice the capacity (250 mAh g −1) as that of c-Na 2TiS 3 (140 mAh g −1) and the inserted and extracted sodium amounts of a-Na 2TiS 3 were similar to that of amorphous TiS 3.
We have compared their structural and electrochemical characters. In this letter, we synthesized crystalline Na 2TiS 3 ( c-Na 2TiS 3) and amorphous Na 2TiS 3 ( a-Na 2TiS 3) as sodium containing sulfides.
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Structural flexibility and free volume resulting from amorphization would be also effective in improving the deintercalation of sodium ion from sodium containing active materials. Sodium containing polysulfide Na 2TiS 3 was also expected to be a high capacity active material with similar performance to TiS 3. 14 Sodium containing polysulfides as active materials for sodium batteries provide an extended choice of negative electrodes, however there are few reports about them. 9 We have also reported that amorphous TiS 3 showed high capacity in an all-solid-state sodium battery. reported that amorphization of TiS 3 suppressed irreversible structure change and led to an increase in reversible capacity. suggested the advantages of amorphous active materials were attributed to their structural defects and free volume. Moreover, cells using amorphous MoS 2 show not only higher capacity but also better rate performance than cells with crystalline materials. It has been reported that amorphization is effective for improving reversibility of TiS 3, 9, 11 MoO 2 12 and V 2O 5 13 in lithium secondary batteries. These increased capacities result from involvement of sulfur redox. Ti 3+/Ti 2+ in the lithium ion cells using LiTiS 2 and TiS 2 6 – 10). Cells with transition metal polysulfides show high capacities exceeding the capacity expected from the redox of the transition metal (e.g. 8 In particular, transition metal polysulfides such as Li 2TiS 3 and TiS 3 are candidates for high capacity electrode active materials. One of the keys for the practical use of all-solid-state sodium secondary batteries is the development of suitable electrode active materials with high capacity and cyclability.Ĭonventional transition metal sulfides such as TiS 2 and MoS 2 show high electronic and ionic conductivities 6, 7 and also they work as reversible electrode active materials in lithium or sodium secondary batteries. 1 – 5 These advantages result from non-flammable solid electrolytes and low cost sodium resources. All-solid-state sodium secondary batteries have been regarded as a next generation battery with safety, high energy density, and cost effectiveness arising from abundance of sodium resources. Development of cost effective and highly safe batteries is desired for application to large electrical energy storage such as smart grid systems. Below is a list of accented characters with their name and ALT code.Secondary batteries widely prevail for electrical devices such as laptops, mobile phones, electric vehicles (EVs) and plug-in hybrid EVs (PHEVs).
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