2D transition metal carbides and/or nitrides, so-called MXenes, are noted as ideal fast-charging cation-intercalation electrode materials, which nevertheless suffer from limited specific capacities. Herein, it is reported that constructing redox-active phosphorus-oxygen terminals can be an attractive strategy for Nb4 C3 MXenes to remarkably boost their specific capacities for ultrafast Na+ storage. As revealed, redox-active terminals with a stoichiometric formula of PO2 - display a metaphosphate-like configuration with each P atom sustaining three PO bonds and one PO dangling bond. Compared with conventional O-terminals, metaphosphate-like terminals empower Nb4 C3 (denoted PO2 -Nb4 C3 ) with considerably enriched carrier density (fourfold), improved conductivity (12.3-fold at 300 K), additional redox-active sites, boosted Nb redox depth, nondeclined Na+ -diffusion capability, and buffered internal stress during Na+ intercalation/de-intercalation. Consequently, compared with O-terminated Nb4 C3 , PO2 -Nb4 C3 exhibits a doubled Na+ -storage capacity (221.0 mAh g-1 ), well-retained fast-charging capability (4.9 min at 80% capacity retention), significantly promoted cycle life (nondegraded capacity over 2000 cycles), and justified feasibility for assembling energy-power-balanced Na-ion capacitors. This study unveils that the molecular-level design of MXene terminals provides opportunities for developing simultaneously high-capacity and fast-charging electrodes, alleviating the energy-power tradeoff typical for energy-storage devices.

Chair of Bioanalytical Chemistry Faculty of Chemistry and Food Chemistry Technische Universität Dresden 01062 Dresden Germany

Chair of Solid State and Quantum Chemistry Institute of Inorganic Chemistry RWTH Aachen University D 52056 Aachen Germany

Department of Inorganic Chemistry University of Chemistry and Technology Prague Technická 5 Prague 6 166 28 Czech Republic

Faculty of Chemistry and Food Chemistry and Center for Advancing Electronics Dresden Technische Universität Dresden 01062 Dresden Germany

Faculty of Chemistry University of Warsaw ul Żwirki i Wigury 101 Warsaw 02 089 Poland

Fraunhofer Institute for Ceramic Technologies and Systems Maria Reiche Strasse 2 01109 Dresden Germany

Institute of Ion Beam Physics and Materials Research Helmholtz Zentrum Dresden Rossendorf 01328 Dresden Germany

Leibniz Institute for Solid State and Materials Research Dresden e 5 01069 Dresden Germany

Max Planck Institute for Polymer Research Ackermannweg 10 D 55128 Mainz Germany

Max Planck Institute of Microstructure Physics Weinberg 2 06120 Halle Germany

State Key Laboratory of Metal Matrix Composites School of Materials Science and Engineering Shanghai Jiao Tong University Shanghai 200240 China

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