Scanning electron microscopy indicated that conductive carbon black did not form a good conductive network in the cathode of Li-ion batteries. In contrast, a good conductive network was formed by using wire-like carbon nano-fibers as a conductive additive. These exhibited better electron-transfer ability alleviated the polarization degree, reduced the internal resistance, and improved the electrochemical performance. The electrochemical performance of Li-ion batteries containing the above additives were compared in this paper. The results showed that the performance of a Li-ion battery of 5 mm × 20 mm × 25 mm with carbon nanofiber conductive additive was better than that of a Li -ion battery with carbon black conductive additive.