Revealing the Mechano‐Electrochemical Coupling Behavior and Discharge Mechanism of Fluorinated Carbon Cathodes toward High‐Power Lithium Primary Batteries

Abstract Unclear reaction mechanisms and unsatisfactory power performance hinder the further development of advanced lithium/fluorinated carbon (Li/CF_x) batteries. Herein, the mechano‐electrochemical coupling behavior of a CF_x cathode is investigated by in situ monitoring strain/stress using digital image correlation (DIC) techniques, electrochemical methods, and theoretical equations. The DIC monitoring results present the distribution and dynamic evolution of the plane strain and indicate strong dependence toward the material structure and discharge rate. The average plane principal strain of fully discharged 2D fluorinated graphene nanosheets (FGNSs) at 0.5 C is 0.50%, which is only 38.5% that of conventional bulk‐structure CF_x. Furthermore, the superior structural stability of the FGNSs is demonstrated by the microstructure and component characterization before and after discharge. The plane stress evolution is calculated based on theoretical equations, and the contributions of electrochemical and mechanical factors are examined and discussed. Subsequently, a structure‐dependent three‐region discharge mechanism for CF_x electrodes is proposed from a mechanical perspective. Additionally, the surface deformation of Li/FGNSs pouch cells formed during the discharge process is monitored using in situ DIC. This study reveals the discharge mechanism of Li/CF_x batteries and facilitates the design of advanced CF_x materials.