Selective Lithium Deposition on 3D Porous Heterogeneous Lithiophilic Skeleton for Ultrastable Lithium Metal Anodes

Abstract

Lithium (Li) metal batteries (LMBs) have been deemed as the next promising high‐energy battery systems for ultrahigh energy densities. However, serious Li dendrites and low Coulombic efficiency issues still impede the practical application of LMBs. Herein, a common three‐dimensional (3D) copper foam partially decorated by a thin lithiophilic tin (Sn) layer (CF@Sn) has been constructed as the current collector of a Li metal anode. The large Li ions prefer to be induced by a Sn layer to produce Li−Sn alloy and selectively deposit on the alloy layers of the composite matrix. Due to the excellent confinement of the growth of metallic Li, the 3D porous heterogeneous lithiophilic skeleton can effectively improve uniform Li deposition, inhibit Li dendrite formation, reduce electrolyte consumption and enhance the electrochemical performance. The composite matrix leads to a high Coulombic efficiency (98.5%) over 400 cycles and ultrastable Li charging/discharging behavior for 1000 h for the symmetric cell at 1 mA cm−2. For the low energy barrier of alloy layer, small potential polarization (20 mV in symmetric cell) and nucleation overpotential (10.5 mV) can be obtained as expected. Especially, full cells paired with LiFePO4 cathodes and CF@Sn@Li anodes deliver an enhanced rate capability and a great discharging capacity of 140 mAh g−1 with high capacity retention of 95.2% after 300 cycles at 0.5 C. The proposed 3D lithiophilic skeleton demonstrates an effective strategy to realize stable and practical Li metal anodes.

Strategies to anode protection in lithium metal battery: A review

“…Lithiophilicity can be achieved via other methods, such as letting Li react with metal, metal oxide, or other substances to form a lithophilitic compound. Liu et al constructed a 3D copper foam by depositing a thin lithiophilic tin (Sn) layer on the copper foam (CF) surface, which was accomplished using physical vapor deposition (PVD) 95 . Figure 9(B) shows the Li deposition process on bare CF and composite CF@Sn current collector.…”

“…Copyright 2018, John Wiley and Sons. (B) Schematic illustration of the Li deposition process on bare CF and composite CF@Sn current collector 95 . Reproduced with permission from Reference 95.…”

Nitrogen‐doped Porous Carbon Nanofibers Decorated with Nickel Nanoparticles for Unlocking Low‐cost Structural Lithium Metal Anodes

“…Besides, the 3D host can also adapt to the volume expansion change of the lithium metal. [44][45][46] Designing 3D structural lithium metal anodes is an attractive modification measure. The rational design of structural deposition substrates to induce uniform deposition of lithium metal, thus inhibiting the growth of lithium dendrites and stabilizing the lithium metal anode is the key to realizing lithium metal batteries of high energy density commercially.…”

“…The 3D structural substrate has the advantage of large specific surface area, which is beneficial to reduce the local current density, thereby forming an effective suppression of lithium dendrites. Besides, the 3D host can also adapt to the volume expansion change of the lithium metal [44–46] . Designing 3D structural lithium metal anodes is an attractive modification measure.…”

Preparation and Electrochemical Performance of Reduced Graphene and SnO2 Nanospheres Composite Materials for Lithium‐Ion Batteries and Sodium‐Ion Batteries

“…To solve this problem, we need to exploit electrode materials with high energy density and excellent cycle performance. [4][5][6] In the preparation of batteries, electrode materials and electrolytes play an important role in the overall performance and practical application value of batteries. As the key electrode material, the anode material has always been the research hotspot and focus.…”