Excess surface area in bioelectrochemical systems causes ion transport limitations

We investigated ion transport limitations on 3D graphite felt electrodes by growing Geobacter sulfurreducens biofilms with advection to eliminate external mass transfer limitations. We characterized ion transport limitations by: (i) showing that serially increasing NaCl concentration up to 200 mM increased current linearly up to a total of +273% vs. 0 mM NaCl under advective conditions; (ii) growing the biofilm with a starting concentration of 200 mM NaCl, which led to a maximum current increase of 400% vs. current generation without NaCl, and (iii) showing that un-colonized surface area remained even after steady-state current was reached. After accounting for iR effects, we confirmed that the excess surface area existed despite a non-zero overpotential. The fact that the biofilm was constrained from colonizing and producing further current under these conditions confirmed the biofilms under study here were ion transport-limited. Our work demonstrates that the use of high surface area electrodes may not increase current density when the system design allows ion transport limitations to become dominant.