RESUMEN
Lithium (Li) metal negative electrodes have attracted wide attention for high-energy-density batteries. However, their low coulombic efficiency (CE) due to parasitic electrolyte reduction has been an alarming concern. Concentrated electrolytes are one of the promising concepts that can stabilize the Li metal/electrolyte interface, thus increasing the CE; however, its mechanism has remained controversial. In this work, we used a combination of LiN(SO2F)2 (LiFSI) and weakly solvating 1,2-diethoxyethane (DEE) as a model electrolyte to study how its liquid structure changes upon increasing salt concentration and how it is linked to the Li plating/stripping CE. Based on previous works, we focused on the Li electrode potential (ELi with reference to the redox potential of ferrocene) and solid-electrolyte-interphase (SEI) formation. Although ELi shows a different trend with DEE compared to conventional 1,2-dimethoxyethane (DME), which is accounted for by different ion-pair states of Li+ and FSI-, the ELi-CE plots overlap for both electrolytes, suggesting that ELi is one of the dominant factors of the CE. On the other hand, the extensive ion pairing results in the upward shift of the FSI- reduction potential, as demonstrated both experimentally and theoretically, which promotes the FSI--derived inorganic SEI. Both ELi and SEI contribute to increasing the Li plating/stripping CE.
RESUMEN
Unavoidable defects in grain boundaries (GBs) are detrimental and critically influence the organometal halide perovskite performance and stability. To address this issue, semiconducting molecules have been employed to passivate traps along perovskite GBs. Here, we designed and synthesized three squaraine molecules (SQ) with zwitterionic structure to interact with under-coordinated Pb2+ and passivate Pb-I antisite defects. Density functional theory calculation shows symmetric O atoms could coordinate with perovskite grains simultaneously, resulting in continuous charge distribution at the SQ-perovskite interface. The energetic traps distribution in CH3NH3PbI3 perovskite is influenced significantly by the interaction between SQ and perovskite as analyzed by thermally stimulated current, in which the deep-level defects are considerably reduced due to efficient SQ passivation. In addition, we explore how SQ molecules with different energy offset affect the charge extraction, which is suggested to facilitate exciton separation at the perovskite-SQ interface. These benefits lead to enhanced perovskite efficiency from 15.77 to 18.83% with the fill factor approaching 80%, which is among the highest efficiency reported for MAPbI3 solar cells fabricated in an ambient environment at 60% relative humidity (RH). Considerable retardation of perovskite device degradation was achieved, retaining 90% of initial efficiency when kept 600 h at 60 ± 5% RH.