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New 4V-Class and Zero-Strain Cathode Material for Na-Ion Batteries

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journal contribution
posted on 21.08.2017, 00:00 by Jongsoon Kim, Gabin Yoon, Myeong Hwan Lee, Hyungsub Kim, Seongsu Lee, Kisuk Kang
Here, we introduce Na3V­(PO3)3N as a novel 4V-class and zero-strain cathode material for Na-ion batteries. Structural analysis based on a combination of neutron and X-ray diffraction (XRD) reveals that the Na3V­(PO3)3N crystal contains three-dimensional channels that are suitable for facile Na diffusion. The Na (de)­intercalation is observed to occur at ∼4 V vs Na/Na+ in the Na cell via the V3+/V4+ redox reaction with ∼67% retention of the initial capacity after over 3000 cycles. The remarkable cycle stability is attributed to the near-zero volume change (∼0.24%) and unique centrosymmetric distortion that occurs during a cycle despite the large ionic size of Na ions for (de)­intercalation, as demonstrated by ex situ XRD analysis and first-principles calculations. We also demonstrate that the Na3V­(PO3)3N electrode can display outstanding power capability with ∼84% of the theoretical capacity retained at 10C, even though the particle sizes are on the micrometer scale (>5 μm), which is attributed to its intrinsic three-dimensional open-crystal framework. The combination of this high power capability and extraordinary cycle stability makes Na3V­(PO3)3N a new potential cathode material for Na-ion batteries.

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