Disrupting the Crystal Growth of Corrosion Byproducts to Stabilize Aqueous Zn Metal Batteries.

There is a key missing point in the research field of zinc metal batteries (ZMBs); that is, no one pays attention to the crystal growth of byproducts. In this paper, from the perspective of crystallography, a method of disturbing the crystal growth of corrosion byproducts is proposed to improve the serious water-related corrosion in ZMBs. In consideration of the thermodynamics and dynamics of crystallization, the corrosion inhibitor (CI) molecules are introduced to envelop the active growth sites of byproduct crystals and increase the surface free energy change (ΔGs), thus leading to a positive free energy change (ΔG) unfavorable for crystal formation and growth. Therefore, the expansion of the crystal lattice (that is, crystal growth) is impeded, resulting in the distortion and inhibition of the byproduct crystal structure, which have been comprehensively validated through density functional theory (DFT) calculations and in situ X-ray diffraction (XRD) measurements. Extensive research is also conducted on various CI compounds with an adjusted number of phosphate groups and carbon chain length. This work innovatively focuses on inhibiting the crystallization process of byproducts, which is of great significance for the study of water-related corrosion, showcasing the significant potential in enhancing the longevity of aqueous batteries.