Breakthroughs in high-capacity anodes represent a critical frontier in the development of next-generation high-specific-energy storage systems. However, the current high-capacity anodes of lithium batteries are confronted with numerous challenges, including uncontrolled volume expansion, lithium dendrite growth, dead lithium, and unstable solid electrolyte interphase (SEI) films. Herein, we firstly employ laser engraving technology to fabricate an ultra-light freestanding graphene film with through-hole array and defect-rich edges, which serves as a lithium-free anode that integrates lithium-ion intercalation and metallic lithium deposition. During discharge, the defect structures at the pore edges facilitate the adsorption of lithium ions and their rapid intercalation between graphene layers, forming the LiC_x framework. This enables the conversion of quasi-dead lithium through the solid-state pathway of Li → LiC_x → Li⁺. Simultaneously, the vertically aligned through-holes homogenize ion flux and promote metallic lithium storage within the pores, thereby achieving high areal capacity, excellent reversibility, dendrite-free growth, and minimal volume change. As a result, this ultra-light freestanding lithium-free graphene anode (FLFGA) achieves highly reversible Li storage with 99.9% Coulombic efficiency (CE) over 1300 cycles and dendrite-free plating/stripping at a high areal capacity of 4 mAh·cm⁻² (1350 mAh·g⁻¹ anode). When paired with a high-loading LiFePO₄ (LFP) cathode (11.5 mg·cm⁻²), the FLFGA||LFP full cell exhibits significantly enhanced cycling stability (500 cycles), outperforming most conventional Li metal battery, lean-Li battery, and anode-free Li battery systems. This work demonstrates a viable lithium-free anode strategy via laser-engraved graphene engineering, paving the way for durable, safe, and high-energy-density Li batteries.

Transition metal dichalcogenides (TMDs) have been regarded as promising cathodes for aqueous zinc-ion batteries (AZIBs) but suffer from sluggish reaction kinetics due to their poor conductivity and the strong electrostatic interaction between Zn-ion and cathode materials. Herein, a well-defined structure with MoSSe nanosheets vertically anchored on graphene is used as the cathode for AZIBs. The dissolution of Se into MoS₂ lattice together with heterointerface design via developing C–O–Mo bonds improves the inherent conductivity, enlarges interlayer spacing, and generates abundant anionic vacancies. As a result, the Zn²⁺ intercalation/deintercalation process is greatly improved, which is confirmed by theoretical modeling and ex-situ experimental results. Remarkably, the assembled AZIBs exhibit high-rate capability (124.2 mAh·g⁻¹ at 5 A·g⁻¹) and long cycling life (83% capacity retention after 1,200 cycles at 2 A·g⁻¹). Moreover, the assembled quasi-solid-state Zn-ion batteries demonstrate a stable cycling performance over 100 cycles and high capacity retention over 94% after 2,500 bending cycles. This study provides a new strategy to unlock the electrochemical activity of TMDs via interface design and atomic engineering, which can also be applied to other TMDs for multivalent batteries.