A Three-Dimensional Nano-web Scaffold of Ferroelectric Beta-PVDF Fibers for Lithium Metal Plating and Stripping

Lithium metal has been considered as an anode material to improve energy densities of lithium chemistry-based rechargeable batteries (that is to say, lithium metal batteries or LMBs). Higher capacities and cell voltages are ensured by replacing practically used anode materials such as graphite with lithium metal. However, lithium metal as the LMB anode material has been challenged by its dendritic growth, electrolyte decomposition on its fresh surface, and its serious volumetric change. To address the problems of lithium metal anodes, herein, we guided and facilitated lithium ion transport along a spontaneously polarized and highly dielectric material. A three-dimensional web of nanodiameter fibers of ferroelectric beta-phase polyvinylidene fluoride (beta-PVDF) was loaded on a copper foil by electrospinning (PVDF#Cu). The electric field applied between the nozzle and target copper foil forced the dipoles of PVDF to be oriented centro-asymmetrically and then the beta structure induced ferroelectric polarization. Three-fold benefits of the ferroelectric nano-web architecture guaranteed the plating/stripping reversibility especially at high rates: (1) three-dimensional scaffold to accommodate the volume change of lithium metal during plating and stripping, (2) electrolyte channels between fibers to allow lithium ions to move, and (3) ferroelectrically polarized or negatively charged surface of beta-PVDF fibers to encourage lithium ion hopping along the surface. Resultantly, the beta-PVDF web architecture drove dense and integrated growth of lithium metal within its structure. The kinetic benefit expected from the ferroelectric lithium ion transport of beta-PVDF as well as the porous architecture of PVDF#Cu was realized in a cell of LFP as a cathode and lithium-plated PVDF#Cu as an anode. Excellent plating/stripping reversibility along repeated cycles was successfully demonstrated in the cell even at a high current such as 2.3 mA cm–2, which was not obtained by the nonferroelectric polymer layer.