Direct wetting of Li₇La₃Zr₂O₁₂ electrolyte with molten Li anode and its application in solid-state lithium batteries

Garnet Li6.5La3Zr1.5Ta0.5O12 (LLZTO) is a promising solid electrolyte for solid-state batteries (SSBs) owing to its high ionic conductivity and high chemical/electrochemical stability. However, the solid-to-solid interface between LLZTO electrolyte and Li anode restricts its application. In this work, an in-situ integration of LLZTO electrolyte with Li anode is proposed to solve this problem. Superior to reported works, the LLZTO obtained by our self-consolidation method can be directly wetted by molten Li without any surface treatment. The self-consolidated LLZTO exhibits a dense microstructure consisting of grains and interstitial phases among them, both of which are accessible to molten Li. Removal of surface contaminants on molten Li rather than that on LLZTO is a prerequisite for direct wetting. Benefiting from direct wetting, an intimate interfacial contact between the LLZTO and Li anode is achieved and the interfacial resistance is significantly reduced. The Li symmetric cell exerts a stable Li plating/stripping cycle for 1000 h at 0.20 mA cm(-2) and the solid-state battery paired with LiCoO2 cathode exhibits a capacity retention of 90.0 % at 0.2 C after 200 cycles at room temperature. This work highlights the surface chemistry of electrolyte and electrode, which is crucial for designing their integration and application.