Inner‐Wrinkled Porous Carbons via Soft‐Hard Coupling Assembly Strategy for Ultrahigh‐Capacity Lithium‐Ion Batteries

Abstract Hierarchically porous carbon nanomaterials with precisely tunable architectures hold great promise for advanced electrochemical energy storage/conversion systems, yet their controlled synthesis remains challenging. Herein, a soft‐hard coupling assembly strategy is demonstrated to fabricate 3D inner‐wrinkled porous carbons (IWPCs) via the crosslinking of polyaniline and phytic acid. By tailoring mesoporous silica nanospheres (hard templates) and F127 micelles (soft templates with or without pore expanders), precise control is achieved over the pore structure and carbon skeleton. The optimized carbon material presents a high specific surface area (791 m ² g ⁻¹ ), substantial heteroatom (N/O/P) doping (29.4 wt.%), and abundant defect sites, which synergistically enhance ion transport, active site availability, and electrolyte accessibility. Notably, the unique inner‐wrinkled structure effectively increases Li ⁺ adsorption capacity and mechanical stability. When applied as an anode for lithium ion batteries, the IWPCs deliver an ultrahigh reversible capacity of ≈787 mAh g ⁻¹ at 0.1 A g ⁻¹ , along with superior rate capability, and remarkable cycling stability even at a high current density of 5.0 A g ⁻¹ . This work not only presents a versatile strategy for engineering multiscale porous carbon architectures, but also provides a universal platform for tailoring functional porous materials for energy, environment, and beyond.