Phase Relations and Sodium Ion Conductivity within the Quasi-binary System Na2SiF6/Na2AIF6 . The phase diagram of the Na2SiF6/Na3AlF6 system has been determined by means of x-ray powder diffraction, thermal analysis and conductivity measurements in the sub-solidus region. Na3AlF6 accomodates up to 73 mol.-% Na2SiF6 maintaining the crystal structure type. The sodium ion conductivity increases by about five orders of magnitude upon doping Na3AlF6 with Na2SiF6.