Hierarchical 3D Porous Hydrogen-Substituted Graphdiyne for High-Performance Electrochemical Lithium-Ion Storage

Graphdiyne (GDY) has realized significant achievements in lithium-ion batteries (LIBs) because of its unique π-conjugated skeleton with sp- and sp2-hybridized carbon atoms. Enriching the accessible surface areas and diffusion pathways of Li ions can realize more storage sites and rapid transport dynamics. Herein, three-dimensional porous hydrogen-substituted GDY (HsGDY) is developed for high-performance Li-ion storage. HsGDY, fabricated via a versatile interface-assisted synthesis strategy, exhibits a large specific surface area (667.9 m2 g–1), a hierarchical porous structure, and an expanded interlayer space, which accelerate Li-ion accessibility and lithiation/delithiation. Owing to this high π-conjugated, conductive, and porous framework, HsGDY exhibits a large reversible capacity (930 mA h g–1 after 100 cycles at 1 A g–1), superior cycle (720 mA h g–1 after 300 cycles at 1 A g–1), and rate (490 mA h g−1 at 5 A g–1) performances. Density functional theory calculations of the low diffusion barrier in the lamination and vertical directions further reveal the fast Li-ion transport kinetics of HsGDY. Additionally, a LiCoO2–HsGDY full cell is constructed, which exhibits a good practical charge/discharge capacity of 128 mA h g–1 and stable cycling behavior. This study highlights the advanced design of next-generation LIBs to sustainably develop the new energy industry.