Slight compositional variation-induced structural disorder-to-order transition enables fast Na + storage in layered transition metal oxides.

The omnipresent Na + /vacancy orderings change substantially with the composition that inevitably actuate the ionic diffusion in rechargeable batteries. Therefore, it may hold the key to the electrode design with high rate capability. Herein, the influence of Na + /vacancy ordering on Na + mobility is demonstrated firstly through a comparative investigation in P2-Na 2/3 Ni 1/3 Mn 2/3 O 2 and P2-Na 2/3 Ni 0.3 Mn 0.7 O 2 . The large zigzag Na + /vacancy intralayer ordering is found to accelerate Na + migration in P2-type Na 2/3 Ni 1/3 Mn 2/3 O 2 . By theoretical simulations, it is revealed that the Na + ordering enables the P2-type Na 2/3 Ni 1/3 Mn 2/3 O 2 with higher diffusivities and lower activation energies of 200 meV with respect to the P3 one. The quantifying diffusional analysis further prove that the higher probability of the concerted Na + ionic diffusion occurs in P2-type Na 2/3 Ni 1/3 Mn 2/3 O 2 due to the appropriate ratio of high energy ordered Na ions (Na f ) occupation. As a result, the interplay between the Na + /vacancy ordering and Na + kinetic is well understood in P2-type layered cathodes.