PNNL

Abstract

Lithium metal is an ideal anode for rechargeable lithium battery technology. However, the extreme reactivity of Li-metal with the electrolyte leads to solid electrolyte interphase (SEI) layer which often impedes the Li+ transport across the interface. The challenge is to predict the chemical, structural and topographical heterogeneity of SEI layer arising from multitude of interfacial constituents. Traditionally the pathways and products of electrolyte decomposition processes were analyzed with the basic presumption of pristine Li-metal surface for simplicity. However, ubiquitous inorganic passivation layers on Li-metal can dampen the electronic charge transfer to the electrolyte and significantly alter the SEI layer evolution. In this study, we analyzed the effect of nanometric Li2O, LiOH and Li2CO3 as surface passivation layer on the interfacial reactivity of Li-metal using ab initio molecular dynamics (AIMD) calculations and X-ray photoelectron spectroscopy (XPS) measurements. These nanometric layers impede the electronic charge transfer to the electrolyte and thereby provide some degree of passivation (compared to pristine lithium metal) to the redox based decomposition process. The Li2O, LiOH and Li2CO3 layers admits varying level of electron transfer from Li-metal slab and subsequent storage of the electronic charges within their structure. Nevertheless, their ability for electron transfer to the electrolyte molecules and the extent of bis(trifluoromethanesulfonyl)imide (TFSI) anion decomposition is significantly smaller than that on the pristine Li-metal. The XPS experiments showed that Li2O as major surface component had greater LiF phase formation, whereas a dominant LiOH layer shows enhanced sulfur decomposition process. These observations were explained based on different electronic charge transfer ability of the passivating films derived from AIMD results.