In this work, we combined the DFT calculation and classical MD simulation to investigate the structural, electronic, and dynamic properties of layered P2-type Na-x[Ni1/3Ti2/3]O-2 as bi-functional electrode materials. The effects of cycling on Na-x[Ni1/3Ti2/3]O-2 were studied from the aspect of structural and electronic change during Na insertion and extraction. The expansion of ab plane and contraction of c axis were observed upon Na insertion while the lattice parameter change upon Na extraction was relatively small. Ni and Ti are found to play a dominant role in the redox reactions upon Na extraction and insertion respectively, along with the participation of O. It was found that the electronic and ionic conduction and Na self-diffusion mainly occur along ab plane in the materials. High in-plane ionic conductivity (0.4 similar to 1.4 S/cm) and Na diffusivity (10(-6)similar to 10(-5) cm(2)/s) were observed from 900 to 1200 K, with activation energies of 0.37 and 0.53 eV, respectively. (c) 2018 The Electrochemical Society.