Thick 3D-Printed Hierarchical Li₄Ti₅O₁₂@MOF anode and Grid-Lined micropores for High-Performance Lithium-Ion...

Li₄Ti₅O₁₂ (LTO) anode is a promising candidate for high-energy-density lithium-ion batteries (LIBs), but achieving high mass loading, a porous structure, and efficient ion transport remains a challenge. Herein, we present a high-mass-loading, hierarchically porous LTO anode with a conductive network and grid-lined micropores, embedded with a metal-organic framework (MOF) as both an electrode additive and surface protective layer. This novel structure is fabricated using extrusion-based three-dimensional (3D) printing technology. The self-standing framework provides mechanical stability and high conductivity, enabling a thick (316 microm) 3D-printed LTO@UiO-66-MOF (3D-LTO@U) anode with a mass loading of 11 mg/cm². It delivers a high-rate capability of 161 mAh/g at 5C, an areal specific capacity of 5.37 mAh/cm², and 78.9 % areal capacity retention after 150 cycles. Additionally, it achieves a high specific energy density of 382.35 Wh/kg. The UiO-66 MOF provides strong binding affinity, suppressing side reactions and enhancing Li-ion/electron transport within the 3D-printed interconnected channels. This improves active material utilization during charge and discharge. Furthermore, a 3D-printed full cell integrating a grid-lined 3D-LTO@U anode and a 3D-printed LiFePO₄ cathode exhibits enhanced electrochemical performance. This work demonstrates an effective strategy for designing thick, high-mass-loading, and porous conductive network anodes for advanced LIBs.