Modulating Nanoinhomogeneity at Electrode–Solid Electrolyte Interfaces for Dendrite‐Proof Solid‐State Batteries and Long‐Life Memristors

The penetration of dendrites in ceramic lithium conductors severely constrains the development of solid-state batteries (SSBs) while its nanoscopic origin remain unelucidated. We develop an in-situ nanoscale electrochemical characterization technique to reveal the nanoscopic lithium dendrite growth kinetics and use it as a guiding tool to unlock the design of interfaces for dendrite-proof SSBs. Using Li7La3Zr2O12 (LLZO) as a model system, in-situ nanoscopic dendrite triggering measurements, ex-situ electro-mechanical characterizations, and finite element simulations are carried out which reveal the dominating role of Li+ flux detouring and nano-mechanical inhomogeneity on dendrite penetration. To mitigate such nano-inhomogeneity, an ionic-conductive homogenizing layer based on poly(propylene carbonate) is designed which in-situ reacts with lithium to form a highly conformal interphase at mild conditions. A high critical current density of 1.8mA cm-2 and a low interfacial resistance of 14{\Omega} cm2 is achieved. Practical SSBs based on LiFePO4 cathodes show great cyclic stability without capacity decay over 300 cycles. Beyond this, highly reversible electrochemical dendrite healing behavior in LLZO is discovered using the nano-electrode, based on which a model memristor with a high on/off ratio of ~10^5 is demonstrated for >200 cycles. This work not only provides a novel tool to investigate and design interfaces in SSBs but offers also new opportunities for solid electrolytes beyond energy applications.