Zhang, Xiaoyuan; He, Weihua; Yang, Wulin; Liu, Jia; Wang, Qiuying; Liang, Peng; Huang, Xia; Logan, Bruce E.(Environ. Sci.: Water Res. Technol., Royal Society of Chemistry (RSC), 2016)[Article]
The characteristics of several different types of diffusion layers were systematically examined to improve the performance of activated carbon air cathodes used in microbial fuel cells (MFCs). A diffusion layer of carbon black and polytetrafluoroethylene (CB + PTFE) that was pressed onto a stainless steel mesh current collector achieved the highest cathode performance. This cathode also had a high oxygen mass transfer coefficient and high water pressure tolerance (>2 m), and it had the highest current densities in abiotic chronoamperometry tests compared to cathodes with other diffusion layers. In MFC tests, this cathode also produced maximum power densities (1610 ± 90 mW m−2) that were greater than those of cathodes with other diffusion layers, by 19% compared to Gore-Tex (1350 ± 20 mW m−2), 22% for a cloth wipe with PDMS (1320 ± 70 mW m−2), 45% with plain PTFE (1110 ± 20 mW m−2), and 19% higher than those of cathodes made with a Pt catalyst and a PTFE diffusion layer (1350 ± 50 mW m−2). The highly porous diffusion layer structure of the CB + PTFE had a relatively high oxygen mass transfer coefficient (1.07 × 10−3 cm s−1) which enhanced oxygen transport to the catalyst. The addition of CB enhanced cathode performance by increasing the conductivity of the diffusion layer. Oxygen mass transfer coefficient, water pressure tolerance, and the addition of conductive particles were therefore critical features for achieving higher performance AC air cathodes.
He, Weihua; Zhang, Xiaoyuan; Liu, Jia; Zhu, Xiuping; Feng, Yujie; Logan, Bruce E.(Environ. Sci.: Water Res. Technol., Royal Society of Chemistry (RSC), 2016)[Article]
A new type of scalable MFC was developed based on using alternating graphite fiber brush array anode modules and dual cathode modules in order to simplify construction, operation, and maintenance of the electrodes. The modular MFC design was tested with a single (two-sided) cathode module with a specific surface area of 29 m2 m−3 based on a total liquid volume (1.4 L; 20 m2 m−3 using the total reactor volume of 2 L), and two brush anode modules. Three different types of spacers were used in the cathode module to provide structural stability, and enhance air flow relative to previous cassette (combined anode–cathode) designs: a low-profile wire spacer; a rigid polycarbonate column spacer; and a flexible plastic mesh spacer. The best performance was obtained using the wire spacer that produced a maximum power density of 1100 ± 10 mW m−2 of cathode (32 ± 0.3 W m−3 based on liquid volume) with an acetate-amended wastewater (COD = 1010 ± 30 mg L−1), compared to 1010 ± 10 mW m−2 for the column and 650 ± 20 mW m−2 for the mesh spacers. Anode potentials were unaffected by the different types of spacers. Raw domestic wastewater produced a maximum of 400 ± 8 mW m−2 under fed batch conditions (wire-spacers), which is one of the highest power densities for this fuel. Over time the maximum power was reduced to 300 ± 10 mW m−2 and 275 ± 7 mW m−2 for the two anode compartments, with only slightly less power of 250 ± 20 mW m−2 obtained under continuous flow conditions. In fixed-resistance tests, the average COD removal was 57 ± 5% at a hydraulic retention time of 8 h. These results show that this modular MFC design can both simplify reactor construction and enable relatively high power generation from even relatively dilute wastewater.
A larger (6.1 L) MFC stack made in a scalable configuration was constructed with four anode modules and three (two-sided) cathode modules, and tested at a wastewater treatment plant for performance in terms of chemical oxygen demand (COD) removal and power generation. Domestic wastewater was fed either in parallel (raw wastewater to each individual anode module) or series (sequentially through the chambers), with the flow direction either alternated every one or two days or kept fixed in a single direction over time. The largest impact on performance was the wastewater COD concentration, which greatly impacted power production, but did not affect the percentage of COD removal. With higher COD concentrations (∼500 mg L−1) and alternating flow conditions, power generation was primarily limited by the cathode specific area. In alternating flow operation, anode modules connected to two cathodes produced an average maximum power density of 6.0 ± 0.4 W m−3, which was 1.9 ± 0.2 times that obtained for anodes connected to a single cathode. In fixed flow operation, a large subsequent decrease in COD influent concentration greatly reduced power production independent of reactor operation in parallel or serial flow modes. Anode modules connected to two cathodes did not consistently produce more power than the anodes connected to a single cathode, indicating power production became limited by restricted anode performance at low CODs. Cyclic voltammetry and electrochemical impedance spectroscopy data supported restricted anode performance with low COD. These results demonstrate that maintaining power production of MFC stack requires higher influent and effluent COD concentrations. However, overall performance of the MFC in terms of COD removal was not affected by operational modes.
He, Weihua; Yang, Wulin; Tian, Yushi; Zhu, Xiuping; Liu, Jia; Feng, Yujie; Logan, Bruce(Journal of Power Sources, Elsevier BV, 2016-09-30)[Article]
Large differences between the water and air pressure in microbial fuel cells (MFCs) can deform and damage cathodes. To avoid deformation, the cathode air pressure was controlled to balance pressure differences between the air and water. Raising the air pressures from 0 to 10 kPa at a set cathode potential of −0.3 V (versus Ag/AgCl) enhanced cathode performance by 17%, but pressures ≥25 kPa decreased current and resulted in air leakage into the solution. Matching the air pressure with the water pressure avoided cathode deformation and improved performance. The maximum power density increased by 15%, from 1070 ± 20 to 1230 ± 70 mW m, with balanced air and water pressures of 10–25 kPa. Oxygen partial pressures ≥12.5 kPa in the cathode compartment maintained the oxygen reduction rate to be within 92 ± 1% of that in ambient air. The use of pressurized air flow through the cathode compartments can enable closer spacing of the cathodes compared to passive gas transfer systems, which could make the reactor design more compact. The energy cost of pressurizing the cathodes was estimated to be smaller than the increase in power that resulted from the use of pressurized cathodes.
Microbial fuel cells (MFCs) can generate electricity from the oxidation of organic substrates using anodic exoelectrogenic bacteria and have great potential for harvesting electric energy from wastewater. Improving oxygen reduction reaction (ORR) performance at a neutral pH is needed for efficient energy production. Here we show a nitrogen doped (≈4 wt%) ionothermal carbon aerogel (NDC) with a high surface area, large pore volume, and hierarchical porosity, with good electrocatalytic properties for ORR in MFCs. The MFCs using NDC air cathodes achieved a high maximum power density of 2300 mW m−2, which was 1.7 times higher than the most commonly used Pt/C air cathodes and also higher than most state-of-the-art ORR catalyst air cathodes. Rotating disk electrode measurements verified the superior electrocatalytic activity of NDC with an efficient four-electron transfer pathway (n=3.9). These findings highlight NDC as a better-performing and cost-efficient catalyst compared with Pt/C, making it highly viable for MFC applications.
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