Self‐Standing 3D Cathodes for All‐Solid‐State Thin Film Lithium Batteries with Improved Interface Kinetics

3D all-solid-state thin film batteries (TFBs) are proposed as an attractive power solution for microelectronics. However, the challenge in fabricating self-supported 3D cathodes constrains the progress in developing 3D TFBs. In this work, 3D LiMn₂ O₄ (LMO) nanowall arrays are directly deposited on conductive substrates by magnetron sputtering via controlling the thin film growth mode. 3D TFBs based on the 3D LMO nanowall arrays and 2D TFBs based on the planar LMO thin films are successfully fabricated using a lithium phosphorous oxynitride (LiPON) electrolyte and Li anode. In comparison, the 3D TFB significantly outperforms the 2D TFB, exhibiting large specific capacity (121 mAh g^-1 at 1 C), superior rate capability (83 mAh g^-1 at 20 C), and good cycle performance (over 90% capacity retention after 500 cycles). The superior electrochemical performance of the 3D TFB can be attributed to the 3D architecture, which not only greatly increases the cathode/electrolyte interface and shortens the Li⁺ diffusion length, but also effectively enhances the structural stability. Importantly, the vertically aligned nanowall array architecture of the cathode can significantly mitigate disordered LMO formation at the cathode surface compared to the 2D planar thin film, resulting in a greatly reduced interface resistance and improved rate performance.