In Situ Construction of a Lithiophilic and Electronically Insulating Multifunctional Hybrid Layer Based on the Principle of Hydrolysis for a Stable Garnet/Li Interface

Adapting solid‐state Li‐metal batteries is an attractive way to pursue higher energy density and safety compared to liquid‐based ones. With high ionic conductivity and excellent stability with Li, Ta‐doped Li7La3Zr2O12 (LLZTO) is an effective option. However, the poor solid–solid interface contact induced by the lithiophobic Li2CO3 layer hinder its practical application. Herein, a versatile strategy is proposed based on the hydrolysis of sodium tetrafluoroborate (NaBF4), aiming to convert the Li2CO3 into multifunctional hybrid layer containing LiF, LiBO2, and NaF. Among them, LiF and LiBO2 serve as the primary Li ion conductors, the introduction of NaF with high surface energy not only enhances the interface wettability, but also further elevates the critical dendrite strength against Li dendrites. All three components serve as excellent electronic insulators, suppressing electron invasion at the interface and preventing Li dendrite growth in the solid electrolyte. As expected, the interfacial impedance of the NaBF4 treated symmetric cell is reduced to 6.0 Ω cm2, the critical current density (CCD) comes to 2.0 mA cm−2, and cycles over 3000 h at 0.3 mA cm−2 and 1500 h at 0.5 mA cm−2 respectively. Besides, the modified SSBs matched with LiFePO4 or LiNi0.6Co0.2Mn0.2O2 cathode show great long‐term cycling and rate performance. A new strategy based on BF4− hydrolysis is proposed for the Garnet/Li interface. This strategy includes high modulus and Lipophilic NaF to inhibit dendrite growth, and high ion conductivities LiF and LiBO2 to regulate lithium‐ion deposition at the interface. Multiple types of functional products cooperate with each other to achieve a stable and low interface resistance interface.