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The Na4VO(PO4)2 phase has been synthesized using a solid state route in sealed tubes. This phase crystallizing in the orthorhombic system has a one-dimensional structure built up of corner shared VO6 and PO4 polyhedra. It is an ionic conductor with a conductivity of 10−4S/cm at 500 K and an activation energy of 0.63eV. The electrochemical properties of Na4VO(PO4)2 as a positive electrode in a sodium...