One-stone, two birds: One step regeneration of discarded copper foil in zinc battery for dendrite-free lithium deposition current collector

Abstract

The ever-growing requirement for electrochemical energy storage has exacerbated the production of spent batteries, and the recycling of valuable battery components has recently received a remarkable attention. Among all battery components, copper foil is widely utilized as a current collector for stable zinc platting and stripping in zinc metal batteries (ZMBs) due to the perfect lattice matching of between metal copper and zinc, which is accompanied by the formation of multiple copper-zinc alloy components during the cycling process. Herein, a novel "two birds with one-stone" strategy through a one simple heat treatment step to revive the discarded copper foil in zinc metal battery is reported to further obtain a lithiophilic current collector (Cu_xZn_y-Cu) with multiple copper-zinc alloy components on the surface of the discarded copper foil. Such revived Cu_xZn_y-Cu current collector greatly reduces the lithium nucleation overpotential and realizes uniform lithium deposition and further inhibits lithium dendrites growth. The formed multiple Cu_xZn_y alloy phases on the surface of discarded copper foil exhibit a low Li nucleation overpotential of only 15 mV at 0.5 mA cm^-2 for the first cycle. Moreover, such a Cu_xZn_y-Cu current collector could achieve stable cycle for 220 cycles at 0.5 mA cm^-2 and 110 cycles at 1 mA cm^-2 with a Li plating capacity of 1 mAh cm^-2. Theoretical calculations indicate that, compared with pure Cu foil, the formed multiple alloy components of CuZn₅, CuZn₈, Cu_0.61Zn_0.39 and CuZn have low adsorption energy of -2.17, -2.55, -2.16 and -2.35 eV with lithium atoms, respectively, which result in reduced lithium nucleation overpotential. The full cell composed of Cu_xZn_y alloy current collector with deposition of 5 mAh cm^-2 metal Li anode coupled with LiFePO₄ (LFP) cathode exhibits a reversible capacity of 125.6 mAh/g after 110 cycles at a current of 0.5 C with capacity retention of 85.1 %. This work proposed a promising strategy to regenerate the discarded copper foil in rechargeable batteries.

Keywords: Copper foil current collector; Lithiophilicity; Lithium metal batteries; Multi-component copper-zinc alloys; Zinc metal batteries.