biostudies-literatureShi YNational Science Foundation of China | National Natural Science Foundation of China-Yunnan Joint FundNational Science Foundation of China | National Natural Science Foundation of China-Yunnan Joint Fund (NSFC-Yunnan Joint Fund)National Natural Science Foundation of ChinaNatural Science Foundation of Guangdong ProvinceNatural Science Foundation of Guangdong Province (Guangdong Natural Science Foundation)National Natural Science Foundation of China (National Science Foundation of China)National Key Research and Development Project7888https://www.ebi.ac.uk/biostudies/studies/S-EPMC9780345biostudies-literatureUnknown13(1)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_2/3Ni_1/3Mn_2/3O₂ and P2-Na_2/3Ni_0.3Mn_0.7O₂. The large zigzag Na⁺/vacancy intralayer ordering is found to accelerate Na⁺ migration in P2-type Na_2/3Ni_1/3Mn_2/3O₂. By theoretical simulations, it is revealed that the Na⁺ ordering enables the P2-type Na_2/3Ni_1/3Mn_2/3O₂ 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_2/3Ni_1/3Mn_2/3O₂ 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.Nature communicationsSlight compositional variation-induced structural disorder-to-order transition enables fast Na⁺ storage in layered transition metal oxides.PMC97803452021B151512000222075328221091862022A1515010405Qian GYin WWei BLu XWang SChen WChen HKan WHSun YShi YJiang PfalseSlight 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_2/3Ni_1/3Mn_2/3O₂ and P2-Na_2/3Ni_0.3Mn_0.7O₂. The large zigzag Na⁺/vacancy intralayer ordering is found to accelerate Na⁺ migration in P2-type Na_2/3Ni_1/3Mn_2/3O₂. By theoretical simulations, it is revealed that the Na⁺ ordering enables the P2-type Na_2/3Ni_1/3Mn_2/3O₂ 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_2/3Ni_1/3Mn_2/3O₂ 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.2022-01-01T00:00:00Z2022 Dec2026-06-03T13:23:03.418Z2025-04-06T08:26:45.898ZS-EPMC97803453655012810.1038/s41467-022-35597-4