Using cyclic voltammetry (CV), in‐situ scanning tunneling microscopy (STM) and electrochemical quartz crystal microbalance (EQCM) the initial stages of lithium deposition on Au(111) from a solution of lithium bis(trifluoromethylsulfonyl)imide in the commercially available ionic liquid 1‐methyl‐1‐propylpiperidinium bis(trifluoromethylsulfonyl)imide (MPPipTFSI) were investigated. We could identify three distinct cathodic peaks in the potential range from 0 to −2.5 V (vs. Pt quasi‐reference electrode), corresponding to different lithium deposition modes. While in the potential region of the under‐potential deposition (UPD) (−1.2 to −1.8 V) the growth of monoatomic high islands (300–370 pm) takes place, Li bulk deposition occurs at potentials <−2.3 V. Finally, the third peak at 0 V, which only appears after a previous bulk deposition, is connected to a strand‐like growth of lithium at (111) terraces with a uniform orientation over the whole substrate. Interestingly, once reaching a step‐edge, the one‐dimensional growth continues into the electrolyte, indicating the initial stages of Li dendrite formation.

Silver electrodeposition onto Au(111) has been studied as a function of composition of deep eutectic solvent (DES) type III and IV. The electrochemical investigations were performed by using cyclic voltammetry and in‐situ electrochemical quartz crystal microbalance experiments. Scanning electron microscopy coupled with Auger spectroscopy and atomic force microscopy were used to characterize the deposited metal overlayers. Silver deposition from DES type III shows several analogies to the electrocrystallization from aqueous solutions, such as the presence of underpotential deposition. It is shown that the hydrogen‐bond donor exerts a strong influence on the silver growth mode and on the structure of the metal deposits. In addition, the hydrogen‐bond donor turns out to exert a rather strong influence on the plating process during silver deposition from DES type IV.

The improvement of rechargeable zinc/air batteries was a hot topic in recent years. Predominantly, the influence of water and additives on the structure of the Zn deposit and the possible dendrite formation were studied. However, the effect of the surface structure of the underlying substrate was not focused on in detail, yet. We now show the differences in electrochemical deposition of Zn onto Au(111) and Au(100) from the ionic liquid N‐methyl‐N‐propylpiperidinium bis(trifluoromethanesulfonyl)imide. The fundamental processes were initially characterized via cyclic voltammetry and in situ scanning tunnelling microscopy. Bulk deposits were then examined using Auger electron spectroscopy and scanning electron microscopy. Different structures of Zn deposits are observed during the initial stages of electrocrystallisation on both electrodes, which reveals the strong influence of the crystallographic orientation on the metal deposition of zinc on gold.