Highly ordered TiO2 nanotube arrays (TNAs) modified by other materials with enhanced conductivity and capacitance have been considered to be promising anode materials for supercapacitors. In this work, carbon@TiO2 nanotube arrays (CTNAs) were firstly synthesized through a calcination process under an Ar atmosphere. Then the hierarchical three-dimensional MnO2/carbon@TiO2 nanotube arrays (CMTNAs) were further developed via hydrothermal deposition of uniformly dispersed MnO2 nanoparticles with the help of the in situ reduction effect of the as-obtained carbon layers. The CTNA electrode exhibited a high area capacitance of 5.58 mF cm−2 at a scan rate of 100 mV s−1, which is about 11 times higher than that of the TiO2 nanotube arrays annealed under an air atmosphere (ATNAs). The highest gravimetric capacitance 521.4 A g−1 was achieved with the CMTNAs at a current density of 2 A g−1, and 88.6% of the initial capacitance could be maintained at a current density of 5 A g−1 up to 2000 cycles via a galvanostatic charge–discharge test.
