All-solid-state thin-film lithium-ion batteries are a potential replacement for liquid electrolyte-based Li-ion batteries owing to their superior cycle life, high energy and power densities with an extremely low self-discharge rate at a wide operating temperature range. However, the state-of-art all-solid-state Li-ion batteries mainly use thermal-evaporated lithium metal as anode, which considerably undermines their cost-effectiveness and raises safety concerns of Li explosion. In this study, a layer structure LiCoO₂/lithium phosphorus oxynitride (LiPON)/Si-based all-solid-state Li-ion battery has been successfully developed using sputter-deposition technique. This electrochemical active Li-free all-solid-state Li-ion battery exhibited superior cycling stability from 3.0 to 3.6  V with a wide operating temperature range from -25 to 120ºC. The higher operating temperatures of the LiCoO₂/LiPON/Si-based all-solid-state Li-ion batteries are being investigated and further optimization is currently under way.