Thermal energy was shown to be efficiently converted into electrical power in a thermally regenerative ammonia-based battery (TRAB) using copper-based redox couples [Cu(NH3)42+/Cu and Cu(II)/Cu]. Ammonia addition to the anolyte (2 M ammonia in a copper-nitrate electrolyte) of a single TRAB cell produced a maximum power density of 115 ± 1 W m−2 (based on projected area of a single copper mesh electrode), with an energy density of 453 W h m−3 (normalized to the total electrolyte volume, under maximum power production conditions). Adding a second cell doubled both the voltage and maximum power. Increasing the anolyte ammonia concentration to 3 M further improved the maximum power density to 136 ± 3 W m−2. Volatilization of ammonia from the spent anolyte by heating (simulating distillation), and re-addition of this ammonia to the spent catholyte chamber with subsequent operation of this chamber as the anode (to regenerate copper on the other electrode), produced a maximum power density of 60 ± 3 W m−2, with an average discharge energy efficiency of ∼29% (electrical energy captured versus chemical energy in the starting solutions). Power was restored to 126 ± 5 W m−2 through acid addition to the regenerated catholyte to decrease pH and dissolve Cu(OH)2 precipitates, suggesting that an inexpensive acid or a waste acid could be used to improve performance. These results demonstrated that TRABs using ammonia-based electrolytes and inexpensive copper electrodes can provide a practical method for efficient conversion of low-grade thermal energy into electricity.
2 October 2014 in Environmental Science & Technology Letters
Air cathodes used in microbial fuel cells (MFCs) need to have high catalytic activity for oxygen reduction, but they must also be easy to manufacture, inexpensive, and watertight. A simple one-step, phase inversion process was used here to construct an inexpensive MFC cathode using a poly(vinylidene fluoride) (PVDF) binder and an activated carbon catalyst. The phase inversion process enabled cathode preparation at room temperatures, without the need for additional heat treatment, and it produced for the first time a cathode that did not require a separate diffusion layer to prevent water leakage. MFCs using this new type of cathode produced a maximum power density of 1470 ± 50 mW m–2 with acetate as a substrate, and 230 ± 10 mW m–2 with domestic wastewater. These power densities were similar to those obtained using cathodes made using more expensive materials or more complex procedures, such as cathodes with a polytetrafluoroethylene (PTFE) binder and a poly(dimethylsiloxane) (PDMS) diffusion layer, or a Pt catalyst. Even though the PVDF cathodes did not have a diffusion layer, they withstood up to 1.22 ± 0.04 m of water head (∼12 kPa) without leakage, compared to 0.18 ± 0.02 m for cathodes made using PTFE binder and PDMS diffusion layer. The cost of PVDF and activated carbon ($3 m–2) was less than that of the stainless steel mesh current collector ($12 m–2). PVDF-based AC cathodes therefore are inexpensive, have excellent performance in terms of power and water leakage, and they can be easily manufactured using a single phase inversion process at room temperature.
Differences in microbial fuel cell (MFC) architectures, materials, and solution chemistries, have previously hindered direct comparisons of improvements in power production due to new cathode materials. However, one common reactor design has now been used in many different laboratories around the world under similar operating conditions based on using: a graphite fiber brush anode, a platinum cathode catalyst, a single-chamber cube-shaped (4 cm) MFC with a 3 cm diameter anolyte chamber, 50 mM phosphate buffer, and an acetate fuel. Analysis of several publications over 10 years from a single laboratory showed that even under such identical operational conditions, maximum power densities varied by 15%, with an average of 1.36 ± 0.20 W m−2 (n = 24), normalized to cathode projected area (34 W m−3 liquid volume). In other laboratories, maximum power was significantly less, with an average of 0.91 ± 0.26 W m−2 (n = 10), despite identical conditions. One likely reason for the differences in power is cathode age. Power production with Pt catalyst cathodes significantly declined after one month of operation or more to 0.87 ± 0.31 W m−2 (n = 18) based on studies where cathode aging was examined, while in many studies the age of the cathode was not reported. Using these studies as a performance baseline, we review the claims of improvements in power generation due to new anode or cathode materials, or changes in solution conductivities and substrates.