Gradient Nitrogen Doping in the Garnet Electrolyte for Highly Efficient Solid-State-Electrolyte/Li Interface by N2 Plasma

Solid-state lithium batteries (SSBs) have been widely researched as next-generation energy storage technologies due to their high energy density and high safety. However, lithium dendrite growth through the solid electrolyte usually results from the catastrophic interface contact between the solid electrolyte and lithium metal. Herein, a gradient nitrogen-doping strategy by nitrogen plasma is introduced to modify the surface and subsurface of the garnet electrolyte, which not only etches the surface impurities (e.g., Li₂CO₃) but also generates an in situ formed Li₃N-rich interphase between the solid electrolyte and lithium anode. As a result, the Li/LLZTON-3/Li cells show a low interfacial resistance (3.50 Ω cm²) with a critical current density of about 0.65 mA cm^-2 at room temperature and 1.60 mA cm^-2 at 60 °C, as well as a stable cycling life for over 1300 h at 0.4 mA cm^-2 at room temperature. A hybrid solid-state full cell paired with a LiFePO₄ cathode exhibits excellent cycling durability and rate performance at room temperature. These results demonstrate a rational strategy to enable lithium utilization in SSBs.