This work involves the use of a new type of composite anode system containing SnSb alloy and Li2.6Co0.4N for lithium secondary batteries based on solid polymer electrolytes. The composite electrode shows a high coulombic efficiency (close to 100% even in the first cycle) and a cycle capacity more than 500mAh/g. An addition of LiN(CF3SO2)2 salt into the electrode by direct powder-mixing will decrease its efficiency and capacity. The cycle performance of a cell, using the composite anode and LiNi0.8Co0.2O2 cathode, can be greatly enhanced by modifying the PEO-based polymer electrolyte with BaTiO3 as filler.