Constructing Co₃O₄ Nanowires on Carbon Fiber Film as a Lithiophilic Host for Stable Lithium Metal Anodes

Abstract

Lithium metal has been considered as the most promising anode electrode for substantially improving the energy density of next‐generation energy storage devices. However, uncontrollable lithium dendrite growth, an unstable solid electrolyte interface (SEI), and infinite volume variation severely shortens its service lifespan and causes safety hazards, thus hindering the practical application of lithium metal electrodes. Here, carbon fiber film (CFF) modified by lithiophilic Co3O4 nanowires (denoted as Co3O4 Nws) was proposed as a matrix for prestoring lithium metal through a thermal infusion method. The homogeneous needle‐like Co3O4 nanowires can effectively promote molten lithium to infiltrate into the CFF skeleton. The post‐formed Co−Li2O nanowires produced by the reaction of Co3O4 Nws and molten lithium can homogeneously distribute lithium ions flux and efficaciously increase the adsorption energy with lithium ions proved by density functional theory (DFT) calculation, boosting a uniform lithium deposition without dendrite growth. Therefore, the obtained composite anode (denoted as CFF/Co−Li2O@Li) exhibits superior electrochemical performance with high stripping/plating capacities of 3 mAh cm−2 and 5 mAh cm−2 over long‐term cycles in symmetrical batteries. Moreover, in comparison with bare lithium anode, superior Coulombic efficiencies coupled with copper collector and full battery behaviors paired with LiFePO4 cathode are achieved when CFF/Co−Li2O@Li composite anode was employed.

High-Coulombic-Efficiency Lithium Metal Anodes Enabled by Three-Dimensional Lithiophilic Nanostructures with Multiscale Porosity

“…The enlarged examination in Figure b further confirms the stable and low electrochemical polarization (∼12.0 mV). As summarized in Figure c, these performances surpass those of the recently reported Li composite anodes in LMBs, − confirming the superiority of the NiO/Ni/CC framework enabled by the dual lithiophilicity-pore structure design. By contrast, Li foil and CC-Li cells deliver unstable cycling with high polarizations.…”

“…The CE of the first cycle for the NiO/Ni/CC is 91.7% due to the irreversible SEI layer formation. After the first several cycles, the CE quickly increased to 99.5% and was maintained around 99.97% without any significant drop in the following 800 cycles, which is exceptional for composite Li anodes ,,− ,− (Figure f). The voltage–capacity curves for different cycles (Figure S13) show that the voltage profiles almost coincide for the cycle of 20th, 100th, 200th, 400th, 600th, and 800th.…”

Multifunctional roles of carbon‐based hosts for Li‐metal anodes: A review

“…Metal oxides (ZnO, 86,87 Co 3 O 4 , 83,88 V 2 O 5 , 89 CuO, 90,91 Al 2 O 3 , 92 etc.) particles have also been widely used as functional substance for Li‐metal anodes.…”

Improvement Strategies toward Stable Lithium‐Metal Anodes for High‐Energy Batteries

“…This kind of Li‐metal composite anode has a simple manufacturing process and low cost and is estimated to become a promising applicant for a new generation of higher power battery materials. Besides, metal oxides such as SnO 2 , [97] RuO 2 , [98] Co 3 O 4 [99] and ZnO [100–102] have also been reported to improve the lithium affinity of carbon fibers and regulate the deposition process of lithium ions. To further promote the practical application of composite Li‐metal anodes, Go et al [102] .…”