Ti–Si alloys with the nominal composition of Ti14Si86, Ti16Si84, Ti21Si79 were rapidly solidified using a single roller melt spinning technique. The melt-spun Ti–Si ribbon powders were mechanically milled with graphite powders, followed by the carbon coating through pyrolysis of coal tar pitch at 900°C under argon flow. These composite electrodes exhibit good cycle performance, especially when the Si content in the Ti–Si alloy is below the composition of the Si+TiSi2 eutectic.