Two-dimensional conductive metal-organic frameworks (2D c-MOFs) with high electrical conductivity and tunable structures hold significant promise for applications in metal-ion batteries. However, the construction of 3D interpenetrated c-MOFs for applications in metal-ion batteries is rarely reported. Herein, a 3D four-fold interpenetrated c-MOF (Cu-DBC) constructed by conjugated and contorted dibenzo[g,p]chrysene-2,3,6,7,10,11,14,15-octaol (DBC) ligands is explored as an advanced cathode material for sodium-ion batteries (SIBs) for the first time. Notably, the expanded conjugated and four-fold interpenetrating structure endows Cu-DBC with transmission channels for electrons and sufficient spacing for sodium ion diffusion. As expected, the Cu-DBC cathode showcases higher specific capacity (120.6 mA h g-1, 0.05 A g-1) and robust cycling stability (18.1% capacity fade after 4000 cycles, 2 A g-1). Impressively, the Cu-DBC cathode also exhibits good electrochemical properties at extreme temperatures (-20 °C and 50 °C). A series of in/ex situ characterizations and systematic theoretical calculations further reveal the sodium-ion storage mechanism of Cu-DBC, highlighting a three-electron redox process on the redox-active [CuO4] units. This work provides valuable insights for exploring and enriching the applications of 3D interpenetrated c-MOFs in metal-ion batteries.
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