Mechanochemical Synthesis and Structure of the Alkali Metal Magnesium Chalcogenide Na 6 MgS 4 .

The new binary sodium magnesium sulfide was prepared by the mechanochemical synthesis route from Na 2 S and MgS as starting materials. Na 6 MgS 4 is extremely sensitive and partially decomposes in the presence of oxygen traces. With the use of an excess of MgS in the milling process, the molar ratio of the impurities was successfully decreased from 38% (Na 2 S + MgO) to 13% MgO. The crystal structure and properties were characterized by X-ray powder diffraction, thermogravimetry/differential thermal analysis, scanning electron microscopy-energy-dispersive X-ray spectroscopy, and electrochemical impedance spectroscopy. The Rietveld refinement confirmed that Na 6 MgS 4 is isostructural to Na 6 ZnO 4 . The compound crystallized in the hexagonal system in the non-centro-symmetric space group P 6 3 mc (No. 186) with a = 9.0265(1), c = 6.9524(1) Å, V = 490.58(1) Å 3 , and Z = 2. The structure consisted of a wurtzite-like 3D framework built up of corner-sharing MgS 4 and NaS 4 tetrahedra, with 3/4 of the tunnels, parallel to the c axis, filled with octahedrally coordinated sodium atoms. The ionic conductivity of the composite material (87% Na 6 MgS 4 + 13% MgO) being low (4.4 × 10 -8 S cm -1 with E a = 0.56 eV), indium-doped samples Na 6- x □ x Mg 1- x In x S 4 ( x = 0.05, 0.1) were prepared by the mechanochemical synthesis route. These samples also contained 13% MgO. Their ionic conductivities of 9.3 × 10 -8 S cm -1 ( E a = 0.51 eV) and 2.5 × 10 -7 S cm -1 ( E a = 0.49 eV) at 25 °C for x = 0.05 and 0.1, respectively, were higher than the ionic conductivity of the undoped sample.