Hot-pressed PVDF-based Difunctional Protective Layer for Lithium Metal Anodes

doi:10.7503/cjcu20210629

Abstract

Abstract:

Lithium metal has been considered a promising anode for next-generation batteries due to its high specific energy（3860 mA·h/g） and lowest redox potential（-3.04 V vs. SHE）. However， the poor electrochemical stability of lithium metal results in limited cycle life and short-circuit due to lithium dendritic growth. Poor environmental stability of lithium metal also increases production difficulty and cost. Improving the interface stability of lithium metal anode is considered as an important approach to optimize battery performance. Herein， a dual-functional polyvinylidene fluoride（PVDF） protective layer is fabricated on lithium anode surface using a simple hot-pressing method， effectively promoting air stability to 120 min and increasing cycle life of the symmetrical battery to 1200 h. In addition， by introducing SnO₂ nanoparticles， an inorganic-organic composite protective layer is constructed. The composite protective layer induces lithium nucleation sites by in?situ alloying， which greatly reduces lithium plating overpotential to 0.007 V and facilitates better cyclability of lithium metal anodes. The full-cell with this protective layer shows a long cycle life of 200 cycles with a capacity retention rate higher than 90% and a high discharge capacity of 127 mA·h/g at a current rate of 3C. The strategy proposed in this work for the dual-function interface protective layer can effectively improve the air stability and electrochemical performance of lithium metal anode.

Key words: Lithium metal anode, Surface protective layer, Polyvinylidene fluoride, In?situ alloying, Air stability

CLC Number:

O646

TrendMD:

LI Weihui, LI Haobo, ZENG Cheng, LIANG Haoyue, CHEN Jiajun, LI Junyong, LI Huiqiao. Hot-pressed PVDF-based Difunctional Protective Layer for Lithium Metal Anodes[J]. Chem. J. Chinese Universities, 2022, 43(2): 20210629.

Figures/Tables 8

Scheme 1 PVDF?based protective layer for lithium metal anodes and heating and pressing method

Fig.1 Cross?sectional SEM image of the PVDF protective layer(A), surface SEM images of external surface(B) and internal surface(C) closing to the lithium anode of the PVDF protective layer and FTIR spectrum of PVDF membrane(D)

Fig.2 Optical images taken after different time of exposure in air(A), mass evolution with time of exposure in air of Li@PVDF and bare lithium metal anodes(B) and EIS plots of the specimens of Li@PVDF and bare lithium metal anodes before and after 2 h exposure in air(C)

Fig.3 Side(A, B) and surface(C,D) SEM images of the bare lithium metal(A,C) and Li@PVDF anodes(B,D) after cycling, galvanostatic cycle(DC) of symmetrical cells based on bare lithium metal and protected Li@PVDF anodes at 1 mA/cm2 and 1 mA·h/cm2(E), with magnified profile showing initial stage(F) and stable cycling stage(G)

Fig.4 XRD patterns of nano?SnO2, PVDF membrane, SnO2?PVDF composite membrane and Li@PVDF?SnO2 anode(A), external(B) and internal(C) surface SEM images of Li@PVDF?SnO2 anode

Scheme 2 In?situ alloying on lithium metal surface during heating and pressing

Fig.5 Galvanostatic cycle of symmetrical cells based on bare Li, Li@PVDF and Li@PVDF?SnO2 anodes at 1 mA/cm2 and 1 mA·h/cm2(A), with magnified profile showing initial stage(B) and stable cycling stage(C)

Fig.6 Comparison of cycle performances(A), charge?discharge curves at 1st and 200th cycles(B) and rate performance of full?cells between bare Li and Li@PVDF?SnO2 anodes(C)

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