A Stress Self‐Adaptive Silicon/Carbon “Ordered Structures” to Suppress the Electro‐Chemo‐Mechanical Failure: Piezo‐Electrochemistry and Piezo‐Ionic Dynamics

Construction of ordered structures that respond rapidly to environmental stimuli has fascinating possibilities for utilization in energy storage, wearable electronics, and biotechnology. Silicon/carbon (Si/C) anodes with extremely high energy densities have sparked widespread interest for lithium‐ion batteries (LIBs), while their implementation is constrained via mechanical structure deterioration, continued growth of the solid electrolyte interface (SEI), and cycling instability. In this study, a piezoelectric Bi(0.5)Na(0.5)TiO(3) (BNT) layer is facilely deposited onto Si/C@CNTs anodes to drive piezoelectric fields upon large volume expansion of Si/C@CNTs electrode materials, resulting in the modulation of interfacial Li(+) kinetics during cycling and providing an electrochemical reaction with a mechanically robust and chemically stable substrate. In‐depth investigations into theoretical computation, multi‐scale in/ex situ characterizations, and finite element analysis reveal that the improved structural stability, suppressed volume variations, and controlled ion transportation are responsible for the improvement mechanism of BNT decorating. These discoveries provide insight into the surface coupling technique between mechanical and electric fields to control the interfacial Li(+) kinetics behavior and improve structural stability for alloy‐based anodes, which will also spark a great deal attention from researchers and technologists in multifunctional surface engineering for electrochemical systems.