Rechargeable sodium batteries—VI. Cycling behavior of VS2, ‘VCl3 + nS’ and NbS2Cl2 cathodes in molten NaAlCl4

The electrochemistry of VS₂ in molten NaAlCl₄ has been investigated in relation to its usefulness as a reversible positive electrode for sodium batteries operating in the moderate temperature range of 160–200°C. VS₂ reacted with NaAlCl₄ during early stages of cell cycling, and became VS₂Cl showing a reversible capacity of 2.8 electrons/vanadium. The electrochemistry of mixtures of VCl₃ and S in molten NaAlCl₄ showed similarities to that of VS₂Cl. The VS_xCl_y cathodes obtained via the two different routes exhibited excellent rechargeability as evidenced by the long-term cycling behavior of cells of the configuration, Na_(l)/β″-Al₂O₃/NaAlCl_4(l), cathode material. When NbS₂Cl₂ was used as the cathode material it underwent a structural change in the first cycle to form what appeared to be NbS₂Cl₂, the Nb analog of VS_xCl_y. The structurally modified niobium sulfur chloride cathode exhibited excellent rechargeability.