Reactive Magnesium Nitride Additive: A Drop‐in Solution for Lithium/Garnet Wetting in All‐Solid‐State Batteries

Abstract Garnet oxides such as Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) are promising solid electrolyte materials for all‐solid‐state lithium‐metal batteries because of high ionic conductivity, low electronic leakage, and wide electrochemical stability window. While LLZTO has been frequently discussed to be stable against lithium metal anode, it is challenging to achieve and maintain good solid‐on‐solid wetting at the metal/ceramic interface in both processing and extended electrochemical cycling. Here we address the challenge by a powder‐form magnesium nitride additive, which reacts with the lithium metal anode to produce well‐dispersed lithium nitride. The in situ formed lithium nitride promotes reactive wetting at the Li/LLZTO interface, which lowers interfacial resistance, increases critical current density (CCD), and improves cycling stability of the electrochemical cells. The additive recipe has been diversified to titanium nitride, zirconium nitride, tantalum nitride, and niobium nitride, thus supporting the general concept of reactive dispersion‐plus‐wetting. Such a design can be extended to other solid‐state devices for better functioning and extended cycle life.