Synthesis of 2D Solid-Solution (NbyV2-y )CTx MXenes and Their Transformation into Oxides for Energy Storage

Vanadium and niobium oxides have been identified as promising electrodes for electrochemical energy storage applications as their constituent transition metals can undergo multiple reduction steps leading to high specific capacities during cycling. MXenes are attractive precursors for these compounds due to their tunable compositions and 2D nanoscale morphology. Herein, we demonstrate the synthesis of a wide range of solid -solution (NbyV2-y)AlC MAX phases, their chemical etching to produce (NbyV2-y)CTx MXenes, and the subsequent oxidation of MXenes to form respective oxides. We show that the formation of solid solutions facilitated the etching kinetics of MAX phase powder and accelerated MXene formation compared to pure vanadium and niobium carbides. Oxidation of V2CTx and Nb2CTx produced bilayered vanadium oxide (BVO) with a crumpled nanosheet morphology and nanostructured amorphous Nb2O5 (nANO) nanospheres, respectively. For oxides derived from solid-solution MXenes, scanning electron microscopy imaging revealed the growth of nANO on the surface of BVO nanosheets. Electrochemical cycling of (NbyV2-y)CTx-derived oxides in Li-ion cells revealed varying intercalation-like behavior with electrodes derived from V2CTx showing redox processes and nANO exhibiting pseudocapacitive response. The CV curves of solid-solution MXene-derived oxides demonstrated primarily BVO/nANO composite-like behavior, with key exceptions. The cells containing Nb0.25V1.75CTx-derived oxide showed a large capacity of 296.8 mA h g(-1) driven by significant electrochemical activity at all potentials along the sweep possibly stemming from niobium doping into BVO structure. The Nb1.00V1.00CTx-derived oxide electrode delivered a specific capacity of 298 mA h g(-1) with contributions from both, BVO and nANO phases. The improved electrochemical stability of (Nb1.00V1.00)CTx-derived oxide electrodes compared to an electrode prepared by physically mixing Nb2CTx -derived oxide with V2CTx -derived oxide with the same Nb/V molar ratio was attributed to the stabilizing effect of the BVO/nANO heterointerface. Our work indicates that the use of solid-solution MXenes as precursors is an attractive strategy to synthesize oxides with compositions, morphologies, and properties that cannot be produced otherwise.