Lithium metal is a potential anode material to develop all-solid-state battery (SSB) with high energy density. However, Li metal easily reacts with atmospheric component (H2O, CO2, O2, N2) and then Li metal must be treated sensitively for industrial applications. Here, we report an inverted-stack Li-free thin-film SSB, SUS/Pt/LiPON/LiCoO2/Au, where highly-crystalline LiCoO2 thin film is formed on amorphous LiPON thin film at room temperature by aerosol deposition and Li metal is electrochemically grown between SUS/Pt and LiPON. The resultant Li-free thin-film SSB operates at 4 V and repeats stable charge-discharge reactions for over 100 cycles at 25 °C.
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