The effect of interface heterogeneity on zinc metal anode cyclability

Zinc metal batteries (ZMBs) are promising candidates for low-cost, intrinsically safe, and environmentally friendly energy storage systems. However, the anode is plagued with problems such as the parasitic hydrogen evolution reaction, surface passivation, corrosion, and a rough metal electrode morphology that is prone to short circuits. One strategy to overcome these issues is understanding surface processes to facilitate more homogeneous electrodeposition of zinc by guiding the alignment of electrodeposited zinc. Using Scanning Electrochemical Microscopy (SECM), the charge transport rate on zinc metal anodes was mapped, demonstrating that manipulating electrolyte concentration can influence zinc electrodeposition and solid electrolyte interphase (SEI) formation in ZMBs. Using XPS and Raman spectroscopy, it is demonstrated that an SEI is formed on zinc electrodes at neutral pH, composed primarily of a Zn₄(OH)₆SO₄·xH₂O species, its formation being attributed to local pH increases at the interface. This work shows that more extended high-rate cycling can be achieved using a 1 M ZnSO₄ electrolyte and that these systems have a reduced tendency for soft shorts. The improved cyclability in 1 M ZnSO₄ was attributed to a more homogeneous and conductive interface formed, rather than the bulk electrolyte properties. This experimental methodology for studying metal battery electrodes is transferable to lithium metal and anode-free batteries, and other sustainable battery chemistries such as sodium, magnesium, and calcium.