research

Atomic and molecular layer deposition (ALD/MLD) coatings are promising solutions for preventing dendrite formation in aqueous and non-aqueous Li/Na/Zn metal batteries. Notably, alumina and alucone coatings have emerged as highly effective against dendrite formation in Zn anodes. Despite their demonstrated efficacy, a comprehensive understanding of their chemo-mechanical impact on anodes remains elusive. In this study, we take a bottom-up framework to these coatings on Zn foils, employing an approach that integrates ab initio simulations with continuum theories to elucidate lattice misfit and chemical bonding. We use this insight to develop a macroscopic model to predict the epitaxial residual stresses generated during thin-film deposition. Our findings reveal a robust chemical bonding between the hydroxylated Zn surface and the thin film. This, in turn, generates large misfit strains that result in significant interfacial stresses during deposition. These results are then compared to experiments by measuring the curvature of the coated thin films, finding good agreement between experiments and theory. This novel understanding sheds light on the fundamental mechanisms underpinning the development of chemo-mechanical stresses in thin films, which impact dendrite suppression in anodes, offering valuable insights for the design of new coatings.

In this study, molecular dynamics (MD) simulations have been performed to explore the variation of ion density and electric potential due to electrode surface modification. Two different surface morphologies, having planer and slit pore with different conditions of surface charge, have been studied for graphene-MnO2 surface using LAMMPS. For different pore widths, the concentration of ions in the double layer is observed to be very low when the surface of the graphene-MnO2 electrode is charged. With a view to identify the optimal pore size for the simulation domain considered, three different widths for the nano-slit type pores and the corresponding ion-ion interactions are examined. Though this effect is negligible for pores with 9.23 and 3.55 Å widths, a considerable increase in the ionic concentration within the 7.10 Å pores is observed when the electrode is kept neutral. The edge region of these nano-slit pores leads to effective energy storage by promoting ion separation and a significantly higher charge accumulation is found to occur on the edges compared to the basal planes. For the simulation domain of the present study, partition coefficient is maximum for a pore size of 7.10 Å, indicating that the ions’ penetration and movement into nano-slit pores are most favorable for this optimum pore size for MnO2-graphene electrodes with aqueous NaCl electrolyte.