Initial Stages of Sodium Deposition onto Au(111) from [MPPip][TFSI]: An In‐Situ STM Study for Sodium‐Ion Battery Electrolytes

Sodium-ion batteries are promising candidates for post-lithium-ion batteries. While sodium has a less negative standard electrode potential compared to lithium, it is still a strong reducing agent. Ionic liquids are suitable solvents for sodium metal batteries, since metallic sodium is very reactive, particularly with water and molecules containing acidic hydrogen atoms. In this study, the initial stages of electrodeposition of sodium on Au(111) from N-methyl-N-propylpiperidinium [MPPip] bis(trifluoromethanesulfonyl)imide [TFSI] were studied using voltammetry and in-situ scanning tunnelling microscopy. Four subsequent underpotential deposition stages were observed: (i) nucleation at the Au(111) reconstruction elbows, followed by (ii) growth of small monoatomically high islands that form (iii) a smooth layer via coalescence, and (iv) further island growth on top of the existing layers. The electrocrystallisation mode changed from smooth layer formation to 3D growth, resulting in cauliflower-like structures. The deposition process was accompanied by simultaneous alloy formation.