PNNL

Abstract

Barite (BaSO4) is a common additive in lead-acid batteries, where it acts as a nucleating agent to promote the reversible formation and dissolution of PbSO4 during battery cycling. However, little is known about the molecular-scale mechanisms the nucleation and cyclic evolution of PbSO4 over a battery’s lifetime. In this study, we explore the responses of a barite (001) surface to cycles of high and low lead concentrations in the presence of 100 mM sulfuric acid using in-situ atomic force microscopy and high-resolution X-ray reflectivity. We find that PbSO4 epitaxial films readily nucleate on the barite surface, even from solutions that are undersaturated relative to bulk PbSO4. Despite this, barite (001) proves to be an ineffective nucleator of bulk PbSO4, as multilayer growth is suppressed even in highly supersaturated solutions. Instead, we find evidence that Pb2+ ions can directly exchange with Ba2+ to create mixed (Ba,Pb)SO4 surfaces. These chemically mixed surfaces do not host PbSO4 monolayers as readily as pristine barite, and the original reactivity is not regained until a fresh surface is reestablished by aggressive etching. Our results can be partly explained by traditional models of Stranski-Krastanov (S-K) growth, in which monolayer films are stabilized by a reduction in surface energy, but multilayer growth is inhibited by epitaxial strain. Complementary density functional theory calculations confirmed the basic energetic-terms of traditional S-K models, but also showed evidence form more complex, thickness-dependent, energetics than would be predicted from the S-K models. The experimental results can be better understood by extending the S-K model to consider the formation of mixed surfaces and films, which can have reduced strain and interfacial energies relative to pure films, while also being stabilized by entropy of mixing. These insights into non-stoichiometric heteroepitaxy will enable better predictions of how barite affects PbSO4 nucleation in battery environments.