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Published on: December 29, 2013
The overshoot phenomenon as a function of internal resistance in microbial fuel cells
Jonathan Winfield1, Ioannis Ieropoulos, John Greenman
1Bristol Robotics Laboratory, University of the West of England, Bristol Business Park, Coldharbour Lane, Bristol BS16 1QD, United Kingdom. jon.winfield@brl.ac.uk
Abstract:
A method for assessing the performance of microbial fuel cells (MFCs) is the polarisation sweep where different external resistances are applied at set intervals (sample rates). The resulting power curves often exhibit an overshoot where both power and current decrease concomitantly. To investigate these phenomena, small-scale (1 mL volume) MFCs operated in continuous flow were subjected to polarisation sweeps under various conditions. At shorter sample rates the overshoot was more exaggerated and power generation was overestimated; sampling at 30 s produced 23% higher maximum power than at 3 min. MFCs with an immature anodic biofilm (5 days) exhibited a double overshoot effect, which disappeared after a sufficient adjustment period (5 weeks). Mature MFCs were subject to overshoot when the anode was fed weak (1 mM acetate) feedstock with low conductivity (<100 μS) but not when fed with a higher concentration (20 mM acetate) feedstock with high conductivity (>1500 μS). MFCs developed in a pH neutral environment produced overshoot after the anode had been exposed to acidic (pH 3) conditions for 24 h. In contrast, changes to the cathode both in terms of pH and varying catholyte conductivity, although affecting power output did not result in overshoot suggesting that this is an anodic phenomenon.
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The interconnection between standard cell potentials and various thermodynamic parameters such as the standard free energy change ΔG° and equilibrium constant K has been previously explored. For example, a redox reaction involving zinc(II) and tin(II) ions at 1 M concentration with Eºcell = +0.291 V and ΔG° = −56.2 kJ is spontaneous.