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Na3V2(PO4)3 (NVP), as a great potential cathode candidate for Na-ion batteries (NIBs), has attracted enormous interest due to its three-dimensional (3D) large open framework for convenient Na+ transport, yet its practical application is still limited by its inferior electron conductivity and sluggish Na+ diffusion kinetics. Herein, the tiny Cr doped hierarchical NVP micro-flower cathodes (i.e., Na3V2−xCrx(PO4)3@C, x ≤ 0.1), which are self-assembled with single-crystal nanoflake subunits in-situ coated with carbon nano-shell, are designed and fabricated via a scalable avenue. The optimized cathode, i.e., Na3V1.94Cr0.06(PO4)3@C (NVCP-6), was endowed with more electro-active Na(2) sites and higher electronic/ionic conductivity for efficient sodium storage. Benefiting from these competitive merits, the NVCP-6, when evaluated as a cathode towards NIBs, exhibits an ultrahigh-rate capability of 99.8 mAh·g−1 at 200 C and superior stability of 82.2% over 7300 cycles at 50 C. Furthermore, the NVCP-6 based full NIBs display remarkable electrochemical properties in terms of both high-rate capacities and long-duration cycling properties at different temperatures (−20–50 °C). The contribution, i.e., the design of “four ounces can move a thousand pounds”, here will promote the practical industrial application of NVP towards advanced NIBs.
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