Enabling High‐Energy Solid‐State Batteries with Stable Anode Interphase by the Use of Columnar Silicon Anodes

All‐solid‐state batteries (ASSBs) with silicon anodes are promising candidates to overcome energy limitations of conventional lithium‐ion batteries. However, silicon undergoes severe volume changes during cycling leading to rapid degradation. In this study, a columnar silicon anode (col‐Si) fabricated by a scalable physical vapor deposition process (PVD) is integrated in all‐solid‐state batteries based on argyrodite‐type electrolyte (Li₆PS₅Cl, 3 mS cm^?1) and Ni‐rich layered oxide cathodes (LiNi_0.9Co_0.05Mn_0.05O₂, NCM) with a high specific capacity (210 mAh g^?1). The column structure exhibits a 1D breathing mechanism similar to lithium, which preserves the interface toward the electrolyte. Stable cycling is demonstrated for more than 100 cycles with a high coulombic efficiency (CE) of 99.7–99.9% in full cells with industrially relevant areal loadings of 3.5 mAh cm^?2, which is the highest value reported so far for ASSB full cells with silicon anodes. Impedance spectroscopy revealed that anode resistance is drastically reduced after first lithiation, which allows high charging currents of 0.9 mA cm^?2 at room temperature without the occurrence of dendrites and short circuits. Finally, in‐operando monitoring of pouch cells gave valuable insights into the breathing behavior of the solid‐state cell.