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Sodium ion batteries have attracted much attention in recent years, due to the higher abundance and lower cost of sodium, as an alternative to lithium ion batteries. However, a major challenge is their lower energy density. In this work, we report a novel multi-electron cathode material, KVOPO4, for sodium ion batteries. Due to the unique polyhedral framework, the V3+ ↔ V4+ ↔ V5+ redox couple was for the first time fully activated by sodium ions in a vanadyl phosphate phase. The KVOPO4 based cathode delivered reversible multiple sodium (i.e. maximum 1.66 Na+ per formula unit) storage capability, which leads to a high specific capacity of 235 Ah kg-1. Combining an average voltage of 2.56 V vs. Na/Na+, a high practical energy density of over 600 Wh kg-1 was achieved, the highest yet reported for any sodium cathode material. The cathode exhibits a very small volume change upon cycling (1.4% for 0.64 sodium and 8.0% for 1.66 sodium ions). Density functional theory (DFT) calculations indicate that the KVOPO4 framework is a 3D ionic conductor with a reasonably, low Na+ migration energy barrier of ≈450 meV, in line with the good rate capability obtained. [ABSTRACT FROM AUTHOR]

Abstract: Sodium ion batteries have attracted much attention in recent years, due to the higher abundance and lower cost of sodium, as an alternative to lithium ion batteries. However, a major challenge is their lower energy density. In this work, we report a novel multi‐electron cathode material, KVOPO4, for sodium ion batteries. Due to the unique polyhedral framework, the V3+ ↔ V4+ ↔ V5+ redox couple was for the first time fully activated by sodium ions in a vanadyl phosphate phase. The KVOPO4 based cathode delivered reversible multiple sodium (i.e. maximum 1.66 Na+ per formula unit) storage capability, which leads to a high specific capacity of 235 Ah kg−1. Combining an average voltage of 2.56 V vs. Na/Na+, a high practical energy density of over 600 Wh kg−1 was achieved, the highest yet reported for any sodium cathode material. The cathode exhibits a very small volume change upon cycling (1.4% for 0.64 sodium and 8.0% for 1.66 sodium ions). Density functional theory (DFT) calculations indicate that the KVOPO4 framework is a 3D ionic conductor with a reasonably, low Na+ migration energy barrier of ≈450 meV, in line with the good rate capability obtained. [ABSTRACT FROM AUTHOR]

In this work, we demonstrate the stable cycling of more than one Li in solid-state-synthesized ε-LiVOPO4 over more than 20 cycles for the first time. Using a combination of density functional theory (DFT) calculations, X-ray pair distribution function (PDF) analysis and X-ray absorption near edge structure (XANES) measurements, we present a comprehensive analysis of the thermodynamics, kinetics, and structural evolution of ε-LixVOPO4 over the entire lithiation range. We identify two intermediate phases at x = 1.5 and 1.75 in the low-voltage regime using DFT calculations, and the computed and electrochemical voltage profiles are in excellent agreement. Operando PDF and EXAFS techniques show a reversible hysteretic change in the short (<2 Å) V-O bond lengths coupled with an irreversible extension of the long V-O bond (>2.4 Å) during low-voltage cycling. Hydrogen intercalation from electrolyte decomposition is a possible explanation for the -2.4 Å V-O bond and its irreversible extension. Finally, we show that ε-LixVOPO4 is likely a pseudo-1D ionic diffuser with low electronic conductivity using DFT calculations, which suggests that nanosizing and carbon coating is necessary to achieve good electrochemical performance in this material. [ABSTRACT FROM AUTHOR]