title: Ab initio study of EMIM-BF4 crystal interaction with a Li (100) surface as a model for ionic liquid/Li interfaces in Li-ion batteries.
abstract: We examined the atomic and electronic structures of an interface between a 1-ethyl-3-methyl imidazolium tetrafluoroborate (EMIM-BF(4)) ionic-liquid crystal and a Li(100) surface by periodic density-functional calculations, as a model for a room-temperature ionic-liquid (RTIL) electrolyte/Li interface at a Li-ion battery electrode. Results are compared with our previous theoretical study of the EMIM-BF(4) molecular adsorption on Li surfaces [H. Valencia et al., Phys. Rev. B 78, 205402 (2008)]. For the EMIM-BF(4) crystal structure, the present projector augmented wave scheme with the generalized gradient approximation can reproduce rather correct intramolecular structures as well as satisfactory short-ranged intermolecular distances, while long-range intermolecular distances are overestimated due to the lack of correct description of long-range dispersive interactions. We constructed a coherent crystal/crystal interface model where four EMIM-BF(4) pairs are stacked on a p(4x3) Li (100) surface cell so as to simulate RTIL-layer deposition on a Li surface. We observed significant attraction of surface Li ions toward contacting BF(4)(-) anions, counterbalanced by electron transfer toward EMIM(+) cations near the interface, revealing the tendency of easy ionization of Li and Li(x)-BF(4) cluster formation, coupled with the reduction of EMIM(+). These features are similar to those observed in the EMIM-BF(4) molecular adsorption, while these have been proved to occur in the crystal-layer adsorption. We examined the adhesive energy, wetability, and detailed electronic structure at the crystal/crystal interface.
authors.affiliation: Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology, 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, Japan. hubert.valencia@aist.go.jp
authors.forename: Hubert
authors.initials: H
authors.lastname: Valencia
authors.forename: Masanori
authors.initials: M
authors.lastname: Kohyama
authors.forename: Shingo
authors.initials: S
authors.lastname: Tanaka
authors.forename: Hajime
authors.initials: H
authors.lastname: Matsumoto