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Research Article

NaF-rich protective layer on PTFE coating microcrystalline graphite for highly stable Na metal anodes

Yangyang Xie1,2,§, Congyin Liu1,§, Jingqiang Zheng1, Huangxu Li3, Liuyun Zhang1, Zhian Zhang1( )
School of Metallurgy and Environment, Engineering Research Center of the Ministry of Education for Advanced Battery Materials, Hunan Provincial Key Laboratory of Nonferrous Value-Added Metallurgy, Central South University, Changsha 410083, China
Ganjiang Innovation Academy, Chinese Academy of Sciences, Ganzhou 341000, China
Department of Chemistry City University of Hong Kong Kowloon, Hong Kong, China

§ Yangyang Xie and Congyin Liu contributed equally to this work.

Show Author Information

Graphical Abstract

The isotropous microcrystalline graphite (MG) with a controllable protective layer by coating poly(tetrafluoroethylene) (PTFE) can be used as Na metal anode host. When plating on Cu foil, due to the absence of effective nucleation sites and protective layer, Na+ flux nonuniform transmission leads to heterogeneous deposition and causes dendrite or dead Na generation. As for MG electrode, owing to the isotropy of MG, Na+ can form co-intercalation to induce Na uniform nucleation and deposition in random direction. But during the long cycling period, for the lack of effective protective layer, the nonuniform deposition can still exist. In contrast, the PTFE coating MG (P@MG) can not only uniform Na nucleation and deposition but also inhibit Na dendrite growth with the PTFE protective later. Thus, P@MG can retain the uniform deposition after many cycles and gain an ultra-stable cycling performance.

Abstract

The practical application of Na metal anode is plagued by the dendrite growth, unstable solid electrolyte interphase (SEI) formation and volume change during the cycling process. Herein, poly(tetrafluoroethylene) (noted as PTFE) coating microcrystalline graphite is designed as the sodium metal anode host by a facile and cost-effective strategy. The isotropous microcrystalline graphite (MG) is conducive to guiding Na+ to form a co-intercalation structure into MG. And the PTFE coating layer can form NaF as artificial SEI film for uniform ion transport and deposition. As a result, the gained PTFE coating MG electrode can deliver a long-life span over 1,200 cycles with an average Coulombic efficiency (CE) of 99.88%. To note, almost the CE in each cycle is around 99.8%–100%. When assembled with Na3V2(PO4)2F3 cathode as full cells, the full cell paired with PTFE coating MG electrode can operate much stable than that of MG electrode for the existence of PTFE coating layer. Even utilized as sodium-free Na metal anode paired with Na3V2(PO4)2F3 cathode, it can also deliver a high initial CE of 76.27% at 0.5 C. After 100 cycles, it still has a high discharge capacity of 83.5 mAh·g−1.

Keywords

co-intercalationNa metal anodespoly(tetrafluoroethylene) (PTFE)microcrystalline graphiteuniform deposition

Electronic Supplementary Material

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Nano Research
Volume 16 Issue 2,
February 2023
Pages 2436-2444
DOI: 10.1007/s12274-022-4985-z
Cite this article:
Xie Y, Liu C, Zheng J, et al. NaF-rich protective layer on PTFE coating microcrystalline graphite for highly stable Na metal anodes. Nano Research, 2023, 16(2): 2436-2444. https://doi.org/10.1007/s12274-022-4985-z
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Received: 22 June 2022
Revised: 14 August 2022
Accepted: 30 August 2022
Published: 01 October 2022
© Tsinghua University Press 2022
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