Electroconvective Flow in Liquid Electrolytes Containing Oligomer Additives.

Metal electrodeposition in batteries is fundamentally unstable and affected by different instabilities depending on operating conditions and electrolyte chemistry. Particularly, at high charging rates, a hydrodynamic instability loosely termed electroconvection sets in, which complicates all electrochemical processes by creating a nonuniform ion flux and preferential deposition at the electrode. Here, we isolate and study electroconvection by experimentally investigating how oligomer additives in liquid electrolytes interact with the hydrodynamic instability at a cation selective interface. From electrochemical measurements and direct visualization experiments, we find that electroconvection is delayed and suppressed at all voltages in the presence of oligomers. The underlying mechanism is revealed to involve formation of an oligomer ad-layer at the interface, which in response to perturbation is believed to exert an opposing body force on the surrounding fluid to preserve the ad-layer structure and in so doing suppresses electroconvection. Our results therefore reveal that in battery electrolytes without obvious sources of bulk elasticity, surface forces produced by adsorbed polymers can be used to advantage for suppressing instability.