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Unlocking fast and reversible sodium intercalation in NASICON Na4MnV(PO4)3 by fluorine substitution
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Unlocking fast and reversible sodium intercalation in NASICON Na4MnV(PO4)3 by fluorine substitution

Jingrong Hou, Mohammed Hadouchi, Lijun Sui, Jie Liu, Mingxue Tang, Wang Hay Kan, Maxim Avdeev, Guiming Zhong, Yi-Kai Liao, Yu-Hong Lai, …
Energy Storage Materials, 卷.42, 頁碼.307-316
11/2021

摘要

23Na solid-state nuclear magnetic resonance Bi-phase mechanism In situ X-ray diffraction Na deficiency NASICON fluorinated phosphate cathode Renewable Energy Sustainability and the Environment Materials Science (all) Energy Engineering and Power Technology
The exploitation of high energy and high power densities cathode materials for sodium ion batteries is a challenge. Na-super-ionic-conductor (NASICON) Na 4 MnV(PO 4 ) 3 is one of promising high-performance and low-cost cathode materials, however, still suffers from not reaching the theoretical capacity, low rate capability, and poor cycling stability. In this work, we deploy a novel sodium-deficient NASICON fluorinated phosphate cathode material for sodium ion batteries which demonstrates, notably, high energy and high power densities concomitant with high sodium diffusion kinetics. The enhanced performance of this novel Na 3.850.15 MnV(PO 3.95 F 0.05 ) 3 cathode was evidenced by demonstrating a relatively high energy density of ∼380 Wh kg −1 at low rate with much improved rate capability compared to non-doped Na 4 MnV(PO 4 ) 3 , and long cycling life over 2000 cycles at high current rates. The structural investigation during battery operation using in situ x-ray diffraction (XRD) reveals bi-phase mechanism with high structural reversibility. The combined XRD and 23 Na nuclear magnetic resonance (NMR) analyses demonstrate that the sodium extraction/insertion from Na2 is faster than Na1 site. These findings open promising prospects for unlocking of high energy and high power densities of NASICON phosphate materials by fluorine substitution towards high-performance sodium ion batteries.

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