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.

Incorporation of multiple inorganics that complement each other can strengthen the efficacy of the SEI layer.

Adding 10 mM KPF6 to the 1 M LiPF6 in ethylene carbonate/dimethyl carbonate electrolyte of symmetrical Li | Li cells eliminated the growth of dendrites at 0.5 mA cm–2 current density and massively reduced, but did not eliminate, the growth of dendrites at 2.5 mA cm–2. The added KPF6 increased the fraction of inorganic salts in the solid electrolyte interface, making it thinner and more Li+ conductive. It overcame the growth of dendrites resulting from inadequate nucleation density but not dendrite growth into the depletion layer, which scales with the layer’s thickness, i.e., the current density.

High resolution analysis shows localized organic-rich impurities in the native Li surface that promote preferential lithium deposition, leading to dendrite growth.