Dual-scale structure engineering synergy enables high-areal-capacity and stable lithium-ion battery anodes

The flourishing electrode materials such as metal oxides have been considered as potential substitutes for next generation lithium-ion batteries (LIBs). However, large stress concentration and inferior mass transfer upon repeated lithiation/delithiation severely compromises the structural integrity of the electrode, especially for high loading thick electrodes. In this work, inspired by the robust bionic thorny structure, we propose a dual-scale structural strategy that integrates macro-architecture with micro-interface to develop a unique yet stable 3D hollow-thorny Cu x O/Cu electrode (3D HT-Cu x O/m-Cu) with stable internal current collector-active material and exterior solid electrolyte interphase (SEI) interfaces. The dense and robust hollow-thorny structure endows the electrode with rapid mass transfer and stress buffering effect that can promote the reaction kinetics. More importantly, the inner semi-coherent Cu-Cu x O interface enables exceptional structural stability and electronic conductivity of the electrode, whereas the exterior inorganic LiF-rich SEI contributes to unblocked Li + transport. Therefore, the designed 3D HT-Cu x O/m-Cu electrode exhibits outstanding Li + diffusion capability (1.25 × 10 -12 cm 2 s -1 ). A high areal capacity of 1.84 mAh cm -2 is achieved even after 250 cycles at 1 mA cm -2 . This study presents a powerful dual-structure engineering strategy to simultaneously mitigate stress concentrations and enhance mass transport, enabling advanced electrodes beyond LIBs. A dual-scale structural strategy integrating macro-architecture and micro-interface is proposed to construct a unique 3D hollow-thorny Cu x O/Cu electrode with robust internal and external interfaces, thereby enabling superior Li + diffusion capability of 1.25 × 10 -12 cm 2 s -1 . • A dual-scale design integrating hollow-thorn structure and semi-coherent Cu–Cu x O interface was developed. • The hollow-thorn framework promotes electrolyte wetting, buffers mechanical stress, and facilitates Li + transport. • The semi-coherent Cu–Cu x O interface ensures robust structural integrity and excellent electronic conductivity. • The electrode delivers high areal capacity of 1.84 mAh cm -2 after 250 cycles with ∼99.9 % Coulombic efficiency.