In the present paper the underpotential deposition (UPD) of lithium on Au(111) from 0.5 mol L−1LiTFSA in the air- and water stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide, [Py1,4]TFSA, has been investigated by cyclic voltammetry (CV) and in situ scanning tunneling microscopy (STM). The pure [Py1,4]TFSA was found to be inert in the potential regime investigated. The results show that the lithium UPD on Au(111) in [Py1,4]TFSA begins at potentials considerably positive to the electrode potential of bulk deposition and follows a layer-by-layer mechanism with the formation of at least two monolayers. A large number of monoatomically deep pits appear when the potential reaches positive values, which is an indication that a Li–Au alloy was formed.
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