Molecular-Level Interfacial Chemistry Regulation of MXene Enables Energy Storage beyond Theoretical Limit

Ti₃C₂T_x MXene often suffers from poor lithium storage behaviors due to its electrochemically unfavorable OH terminations. Herein, we propose molecular-level interfacial chemistry regulation of Ti₃C₂T_x MXene with phytic acid (PA) to directly activate its OH terminations. Through constructing hydrogen bonds (H-bonds) between oxygen atoms of PA and OH terminations on Ti₃C₂T_x surface, interfacial charge distribution of Ti₃C₂T_x has been effectively regulated, thereby enabling sufficient ion-storage sites and expediting ion transport kinetics for high-performance energy storage. The results show that Li ions preferably bind to H-bond acceptors (oxygen atoms from PA), and the flexibility of H-bonds therefore renders their interactions with adsorbed Li ions chemically “tunable”, thus alleviating undesirable localized geometric changes of the OH terminations. Meanwhile the H-bond-induced microscopic dipoles can act as directional Li-ion pumps to expedite ion diffusion kinetics with lower energy barrier. As a result, the as-designed Ti₃C₂T_x/PA achieves a 2.4-fold capacity enhancement compared with pristine Ti₃C₂T_x (even beyond theoretical capacity), superior long-term cyclability (220.0 mAh g^-1 after 2000 cycles at 2.0 A g^-1), and broad temperature adaptability (−20 to 50 °C). This work offers a promising interface engineering strategy to regulate microenvironments of inherent terminations for breaking through the energy storage performance of MXenes.