Zirconium-based metal–organic frameworks/porous carbon hybrids as high-performance anode materials for highly stable lithium- and potassium-ion batteries

Metal-organic framework (MOF)-derived carbon materials have been widely investigated as advanced electrode materials. However, post-synthetic modifications suffer from certain limitations in morphology, surface area, and pore size control. Herein, we report a simple strategy to synthesize surface-confined Zirconium(Zr)-based MOF UiO-66-NH2 carbon hybrids (Zr-MOF@C; denoted as Zr-MOF, Zr-MOF@C10, Zr-MOF@C25, and Zr-MOF@C50) through a covalent assembly/amide linkage between the MOFs and hierarchical porous carbon (PC) in various proportions under solvothermal conditions. Zr-MOF@C hybrids have been utilized as the anode materials for lithium- (LIBs) and potassium-ion batteries (KIBs). In LIBs, the Zr-MOF@C10, Zr-MOF@C25 and Zr-MOF@C50 anodes delivered the discharge capacities of 126, 65 and 94 mA h g−1 at 100 mA g−1 after 100 cycles, respectively. In KIBs, the Zr-MOF@C10 and Zr-MOF@C25 exhibited the high discharge capacities of 78 and 70 mA h g−1 at 100 mA g−1 over 100 cycles. In addition, the Zr-MOF@C25 and Zr-MOF@C50 anodes exhibited an outstanding rate capability with a reversible capacity of ~166 mA h g–1 vs. K+/K and 176 mA h g–1 for Li+/Li, respectively, while well-maintained long-term cyclic stabilities of ~57 mA h g–1 (Zr-MOF@C25 vs. K+/K) and ~140 mA h g–1 (Zr-MOF@C50 vs. Li+/Li) at 1 A g–1 over 1000 cycles. The electrochemical kinetics studies revealed that Li+ and K+ storage efficiencies of all anodes were dominated by a surface-charge capacitive effect and diffusion-driven charge storage mechanism, respectively. These findings provide new insights for designing high-performance surface-confined MOF-based carbon composite materials for next-generation high-energy storage devices.