In Situ Optical Imaging of Sodium Electrodeposition: Effects of Fluoroethylene Carbonate

The morphologies of sodium electrodeposits and gas evolution were studied in a system comprising a symmetrical Na/Na optical cell, a digital microscope, and an electrochemical workstation. Sodium deposition in ethylene carbonate (EC), diethyl carbonate (DEC), and propylene carbonate (PC) generated large volumes of gas and fragile, porous dendrites. The use of fluoroethylene carbonate (FEC) greatly reduced gassing during deposition and demonstrated superior cycling performance, impedance, and cycling efficiency when it was used as a cosolvent with DEC (1:1 vol); however, porous depositions persisted. Time of flight secondary-ion mass spectrometry revealed that the solid-electrolyte interphase formed in FEC/DEC, in contrast with the EC/DEC electrolyte, is thicker, richer in NaF, and forms a less dense polymer organic layer.