Horizontally Asymmetric Nanochannels of Graphene Oxide Membranes for Efficient Osmotic Energy Harvesting.

Abstract

Reverse electrodialysis (RED) directly harvests renewable energy from salinity gradients, and the achievable potential power heavily relies on the ion exchange membranes. Graphene oxides (GOs) are considered a solid candidate for the RED membrane because the laminated GO nanochannels with charged functional groups provide an excellent ionic selectivity and conductivity. Yet, a high internal resistance and poor stability in aqueous solutions limit the RED performance. Here, we develop a RED membrane that concurrently achieves high ion permeability and stable operation based on epoxy-confined GO nanochannels with asymmetric structures. The membrane is fabricated by reacting epoxy-wrapped GO membranes with ethylene diamine via vapor diffusion, overcoming the swelling properties in aqueous solutions. More importantly, the resultant membrane exhibits asymmetric GO nanochannels in terms of both channel geometry and electrostatic surface charges, leading to the rectified ion transport behavior. The demonstrated GO membrane exhibits the RED performance up to 5.32 W·m-2 with >40% energy conversion efficiency across a 50-fold salinity gradient and 20.3 W·m-2 across a 500-fold salinity gradient. Planck-Nernst continuum models coupled to molecular dynamics simulations rationalize the improved RED performance in terms of the asymmetric ionic concentration gradient within the GO nanochannel and the ionic resistance. The multiscale model also provides the design guidelines for ionic diode-type membranes configuring the optimum surface charge density and ionic diffusivity for efficient osmotic energy harvesting. The synthesized asymmetric nanochannels and their RED performance demonstrate the nanoscale tailoring of the membrane properties, establishing the potentials for 2D material-based asymmetric membranes.