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• Charge ordered insulating β-V 2 OPO 4 has been studied. • The charge ordering scenario has been examined. • Phase diagram has been established as a function of correlation strengths. Charge ordering, the ordering of transition metal ions with different oxidation states, is a celebrated feature in mixed valent transition metal oxides, leading to intriguing electronic and magnetic phenomena. In this work, we exploited the electronic and magnetic properties of the charge ordered insulator β-V 2 OPO 4 within the monoclinic C2/c phase by means of first-principles calculations. Our results demonstrated that the AFM-II ordering, in which spin on all V2+ atoms are parallel and so do the spin on all V3+ atoms while these two spin sublattices are antiparallel to each other, experimentally observed, is the magnetic ground state, irrespective of whether the correlation was adopted or not. Furthermore, our theoretical results highlight the importance role of electronic correlation in reasonably reproducing the electronic properties of β-V 2 OPO 4 , including the charge ordering, metal-insulator transition, spin orientation as well as structural distortion. The charge ordering scenario has been analyzed in details in terms of Bader charge, magnetic moments, octahedron volume difference and distortion index. In addition, the phase diagram has been established with respect to correlation strengths. [ABSTRACT FROM AUTHOR]

Understanding the material process and the mechanism behind during battery operation is essential to discover or identify new electrode for the sodium ion batteries. Using first-principles calculations, we systematically investigated the fundamental physical properties, electrochemical activity as well as sodium ion diffusion of the new discovered cathode material, Na 3 V(PO 4) 2. The results identified that the Na+ ion on Na 2 sites is preferentially extracted from the host, which is responsible for the electrochemical redox process, instead of that on Na 1 sites, proposed experimentally. The predicted cell voltage delivers two 'plateaus' with average voltage profile at ~ 3.1 and ~ 3.9 V vs. Na+/Na, corresponding to the V3+/V4+ and V4+/V5+ redox process, respectively, reproducing the experimental observations. Actually, the redox activity of V ions is accompanied with the formation of small polaron as manifested by the magnetic moments and spin density analysis. Furthermore, the fade of the reversible capacity is attributed to the considerable large volume variation (>5%) during the charging-discharging cycling, due to the flexibility of yavapaiite-type layers. The sodium ion diffusion is accomplished through the step-wise ion-exchange mode, in which the Na+ ions originated from both Na 1 and Na 2 sites migrate, progressively and independently, along the a axis between the yavapaiite-type layers, creating a zigzag Na 2 →Na 1 →Na 2 trajectory. Meanwhile, the activation energy is calculated to be reasonable for facile ion diffusion. In addition, the fundamental electronic structures on different charging stages are examined thoughtfully. Our results not only provide a valuable insight on the electronic properties, electrochemical behavior of sodium disintercalation process and diffusion mechanism of Na 3 V(PO 4) 2 , but also inevitably highlight the clues to suppress the large volume variation upon charge/discharge process, and then to improve the cycling capacity. Understanding the material process and the mechanism behind during battery operation is essential to discover or identify new electrode for the sodium ion batteries. Using first-principles calculations, we systematically investigated the fundamental physical properties, electrochemical activity as well as sodium ion diffusion of the new discovered cathode material, Na 3 V(PO 4) 2. Image 1 • Electrochemical properties and sodium ion diffusion in Na 3 V(PO 4) 2 have been explored. • The Na+ ion from Na 2 positions is preferentially extracted from the host, in contrast to the experimental proposition. • The sodium ion diffusion is accomplished through the step-wise ion-exchange mode. • The two-step nature of voltage-composition curve demonstrates that two Na ions participated in the redox reaction. [ABSTRACT FROM AUTHOR]