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Potential sweep and step experiments at microdisk electrodes, radius 4–40 μm, have been used to investigate the nucleation and growth of lithium metal, the anodic dissolution of lithium, the kinetics of the Li/Li+ couple, and the role of surface films in SOCl2/LiAlCl4 . The kinetics of the Li/Li+ couple at freshly deposited Li are fast, and both deposition and dissolution of the metal occur with only small overpotentials. Indeed, under these conditions, the electrochemistry of the system is essentially simple, and the kinetics of the couple are fully described by the Butler‐Volmer equation. Experiments are described which allow the initial stages of film formation to be followed and the influence of such films on lithium deposition and dissolution to be defined. The relationship of these studies to earlier ones carried out at highly filmed lithium surfaces following prolonged contact with SOCl2 (as in a battery) is discussed.

show that the kinetics of the Li/Li+ couple at freshly deposited Li are fast, and both deposition and anodic dissolution of Li in the SOCl2/LiAlCl4 electrolyte occur with only small overpotentials.