Scaling up microbial fuel cells

The goal of this study was to quantify the relation between the surface area of the current-limiting electrode of a microbial fuel cell (MFC) and the power density generated by the MFC. Shewanella oneidensis (MR-1) was grown anaerobically in the anodic compartment of an MFC utilizing lactate as the electron donor. Graphite plate electrodes of various sizes were used as anodes. Commercially available air electrodes, composed of manganese-based catalyzed carbon bonded to a current-collecting screen made of platinum mesh, were used as cathodes, and dissolved oxygen was used as the cathodic reactant. The surface area of the cathode was always significantly larger than that of the anode, to ensure that the anode was the current-limiting electrode. The power density generated by the MFC decreased as the surface area of the anode increased, which fits well with the trend we detected comparing various published results. Thus, our findings bring into question the assertion that the overall power density generated by an MFC with large electrodes can be estimated by extrapolating from an electrode with a small surface area. Our results indicate that the maximum power density generated by an MFC is not directly proportional to the surface area of the anode, but is instead proportional to the logarithm of the surface area of the anode.     

Biological denitrification in microbial fuel cells

Microbial fuel cells (MFCs) that remove carbon as well as nitrogen compounds out of wastewater are of special interest for practice. We developed a MFC in which microorganisms in the cathode performed a complete denitrification by using electrons supplied by microorganisms oxidizing acetate in the anode. The MFC with a cation exchange membrane was designed as a tubular reactor with an internal cathode and was able to remove up to 0.146 kg NO(3-)-N m(-3) net cathodic compartment (NCC) d(-1) (0.080 kg NO(3-)-N m(-3) total cathodic compartment d(-1) (TCC)) at a current of 58 A m(-3) NCC (32 A m(-3) TCC) and a cell voltage of 0.075 V. The highest power output in the denitrification system was 8 W m(-3) NCC (4 W m(-3) TCC) with a cell voltage of 0.214 V and a current of 35 A m(-3) NCC. The denitrification rate and the power production was limited bythe cathodic microorganisms, which only denitrified significantly at a cathodic electrode potential below 0 V versus standard hydrogen electrode (SHE). This is, to our knowledge, the first study in which a MFC has both a biological anode and cathode performing simultaneous removal of an organic substrate, power production, and complete denitrification without relying on H2-formation or external added power.     

Bio-electrodegradation of 2,4,6-Trichlorophenol by mixed microbial culture in dual chambered microbial fuel cells

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Procedure for determining maximum sustainable power generated by microbial fuel cells

Power generated by microbial fuel cells is computed as a product of current passing through an external resistor and voltage drop across this resistor. If the applied resistance is very low, then high instantaneous power generated by the cell is measured, which is not sustainable; the cell cannot deliver that much power for long periods of time. Since using small electrical resistors leads to erroneous assessment of the capabilities of microbial fuel cells, a question arises: what resistor should be used in such measurements? To address this question, we have defined the sustainable power as the steady state of power delivery by a microbial fuel cell under a given set of conditions and the maximum sustainable power as the highest sustainable power that a microbial fuel cell can deliver under a given set of conditions. Selecting the external resistance that is associated with the maximum sustainable power in a microbial fuel cell (MFC) is difficult because the operator has limited influence on the main factors that control power generation: the rate of charge transfer at the current-limiting electrode and the potential established across the fuel cell. The internal electrical resistance of microbial fuel cells varies, and it depends on the operational conditions of the fuel cell. We have designed an empirical procedure to predict the maximum sustainable power that can be generated by a microbial fuel cell operated under a given set of conditions. Following the procedure, we change the external resistors incrementally, in steps of 500 omega every 10, 60, or 180 s and measure the anode potential, the cathode potential, and the cell current. Power generated in the microbial fuel cell that we were using was limited by the anodic current. The anodic potential was used to determine the condition where the maximum sustainable power is obtained. The procedure is simple, microbial fuel cells can be characterized within an hour, and the results of the measurements can serve many purposes, such as: (1) estimating power generation in various MFCs, (2) comparing power generation in MFCs using different electroactive reactants, (3) quantifying the effects of the operational regime on the power generation in MFCs, and finally, (4) the purpose for which the procedure was designed, optimizing the performance of existing MFCs.     

Enhanced power from chambered benthic microbial fuel cells

We describe a new chamber-based benthic microbial fuel cell (BMFC) that incorporates a suspended, high surface area and semi-enclosed anode to improve performance. In Yaquina Bay, OR, two chambered BMFC prototypes generated current continuously for over 200 days. One BMFC was pumped intermittently, which produced power densities more than an order of magnitude greater than those achieved by previous BMFCs with single buried graphite-plate anodes. On average, the continuous power densities with pumping were 233 mW/m2 (2.3 W/m3); peak values were 380 mW/m2 (3.8 W/m3), and performance improved over the time of the deployments. Without pumping, high power densities could similarly be achieved after either BMFC was allowed to rest at open circuit. A third chambered BMFC with a 0.4 m2 footprint was deployed at a cold seep in Monterey Canyon, CA to test the new design in an environment with natural advection. The power density increased 5-fold (140 mW/m2 vs 28 mW/m2) when low-pressure check valves allowed unidirectional flow through the chamber.     

Tubular microbial fuel cells for efficient electricity generation

A tubular, single-chambered, continuous microbial fuel cell (MFC) that generates high power outputs using a granular graphite matrix as the anode and a ferricyanide solution as the cathode is described. The maximal power outputs obtained were 90 and 66 W m(-3) net anodic compartment (NAC) (48 and 38 W m(-3) total anodic compartment (TAC)) for feed streams based on acetate and glucose, respectively, and 59 and 48 W m(-3) NAC for digester effluent and domestic wastewater, respectively. For acetate and glucose, the total Coulombic conversion efficiencies were 75 +/- 5% and 59 +/- 4%, respectively, at loading rates of 1.1 kg chemical oxygen demand m(-3) NAC volume day(-1). When wastewater was used, of the organic matter effectively removed (i.e., 22% at a loading of 2 kg organic matter m(-3) NAC day(-1)), up to 96% was converted to electricity on a Coulombic basis. The lower overall efficiency of the wastewater-treating reactors is related to the presence of nonreadily biodegradable organics and the interference of alternative electron acceptors such as sulfate present in the wastewater. To further improve MFCs, focus has to be placed on the enhanced conversion of nonrapidly biodegradable material and the better directing of the anode flow toward the electrode instead of to alternative electron acceptors. Also the use of sustainable, open-air cathodes is a critical issue for practical implementation.     

Ion exchange membrane cathodes for scalable microbial fuel cells

One of the main challenges for using microbial fuel cells (MFCs) is developing materials and architectures that are economical and generate high power densities. The performance of two cathodes constructed from two low-cost anion (AEM) and cation (CEM) exchange membranes was compared to that achieved using an ultrafiltration (UF) cathode, when the membranes were made electrically conductive using graphite paint and a nonprecious metal catalyst (CoTMPP). The best performance in single-chamber MFCs using graphite fiber brush anodes was achieved using an AEM cathode with the conductive coating facing the solution, at a catalyst loading of 0.5 mg/cm2 CoTMPP. The maximum power densitywas 449 mW/ m2 (normalized to the projected cathode surface area) or 13.1 W/m3 (total reactor volume), with a Coulombic efficiency up to 70% in a 50 mM phosphate buffer solution (PBS) using acetate. Decreasing the CoTMPP loading by 40-80% reduced power by 28-56%, with only 16% of the power (72 mW/m2) generated using an AEM cathode lacking a catalyst. Using a current collector (a stainless steel mesh) pressed against the inside surface of the AEM cathode and 200 mM PBS, the maximum power produced was further increased to 728 mW/m2 (21.2 W/m3). The use of AEM cathodes and brush anodes provides comparable performance to similar systems that use materials costing nearly an order of magnitude more (carbon paper electrodes) and thus represent more useful materials for reducing the costs of MFCs for wastewater treatment applications.     

Capacitive bioanodes enable renewable energy storage in microbial fuel cells

We developed an integrated system for storage of renewable electricity in a microbial fuel cell (MFC). The system contained a capacitive electrode that was inserted into the anodic compartment of an MFC to form a capacitive bioanode. This capacitive bioanode was compared with a noncapacitive bioanode on the basis of performance and storage capacity. The performance and storage capacity were investigated during polarization curves and charge-discharge experiments. During polarization curves the capacitive electrode reached a maximum current density of 1.02 ± 0.04 A/m(2), whereas the noncapacitive electrode reached a current density output of only 0.79 ± 0.03 A/m(2). During the charge-discharge experiment with 5 min of charging and 20 min of discharging, the capacitive electrode was able to store a total of 22,831 C/m(2), whereas the noncapacitive electrode was only able to store 12,195 C/m(2). Regarding the charge recovery of each electrode, the capacitive electrode was able to recover 52.9% more charge during each charge-discharge experiment compared with the noncapacitive electrode. The capacitive electrode outperformed the noncapacitive electrode throughout each charge-discharge experiment. With a capacitive electrode it is possible to use the MFC simultaneously for production and storage of renewable electricity.     

Autotrophic denitrification in microbial fuel cells treating low ionic strength waters

The presence of elevated concentrations of nitrates in drinking water has become a serious concern worldwide. The use of autotrophic denitrification in microbial fuel cells (MFCs) for waters with low ionic strengths (i.e., 1000 μS·cm(-1)) has not been considered previously. This study evaluated the feasibility of MFC technology for water denitification and also identified and quantified potential energy losses that result from their usage. The low conductivity (<1600 μS·cm(-1)) of water limited the nitrogen removal efficiency and power production of MFCs and led to the incomplete reduction of nitrate and the nitrous oxide (N(2)O) production (between 4 and 20% of nitrogen removed). Cathodic overpotential was identified as the main energy loss factors (83-90% of total losses). That high overpotential was influenced by denitrification intermediates (NO(2)(-) and N(2)O) and the potential used by microorganisms for growth, activation, and maintenance.     

Open air biocathode enables effective electricity generation with microbial fuel cells

The reduction of oxygen at the cathode is one of the major bottlenecks of microbial fuel cells (MFCs). While research so far has mainly focused on chemical catalysis of this oxygen reduction, here we present a continuously wetted cathode with microorganisms that act as biocatalysts for oxygen reduction. We combined the anode of an acetate oxidizing tubular microbial fuel cell with an open air biocathode for electricity production. The maximum power production was 83 +/- 11 W m(-3) MFC (0.183 L MFC) for batch-fed systems (20-40% Coulombic yield) and 65 +/- 5 W m(-3) MFC for a continuous system with an acetate loading rate of 1.5 kg COD m(-3) day(-1) (90 +/- 3% Coulombic yield). Electrochemical precipitation of manganese oxides on the cathodic graphite felt decreased the start-up period with approximately 30% versus a non-treated graphite felt. After the start-up period, the cell performance was similar for the pretreated and non-treated cathodic electrodes. Several reactor designs were tested, and it was found that enlargement of the 0.183 L MFC reactor by a factor 2.9-3.8 reduced the volumetric power output by 60-67%. Biocathodes alleviate the need to use noble or non-noble catalysts for the reduction of oxygen, which increases substantially the viability and sustainability of MFCs.     

Tubular membrane cathodes for scalable power generation in microbial fuel cells

One of the greatest challenges for using microbial fuel cells (MFCs) for wastewater treatment is creating a scalable architecture that provides large surface areas for oxygen reduction at the cathode and bacteria growth on the anode. We demonstrate here a scalable cathode concept by showing that a tubular ultrafiltration membrane with a conductive graphite coating and a nonprecious metal catalyst (CoTMPP) can be used to produce power in an MFC. Using a carbon paper anode (surface area Aan = 7 cm2, surface area per reactor volume Aan,s = 25 m2/m3), an MFC with two 3-cm tube cathodes (Acat = 27 cm2, Acat,s = 84 m2/m3) generated up to 8.8 W/m3 (403 mW/m2) using glucose [0.8 g/L in a 50 mM phosphate buffer solution (PBS)], which was only slightly less than that produced using a carbon paper cathode with a Pt catalyst (9.9 W/m3, 394 mW/m2; Acat= 7 cm2, Acat,s= 25 m2/m3). Coulombic efficiencies (CEs) with carbon paper anodes were 25-40% with tube cathodes (CoTMPP), compared to 7-19% with a carbon paper cathode. When a high-surface-area graphite brush anode was used (Aan = 2235 cm2, Aan,s = 7700 m2/m3) with two tube cathodes placed inside the reactor (Acat = 27 cm2, Acas, = 93 m2/m3), the MFC produced 17.7 W/m3 with a CE = 70-74% (200 mM PBS). Further increases in the surface area of the tube cathodes to 54 cm2 (120 m2/m3) increased the total power output (from 0.51 to 0.83 mW), but the increase in volume resulted in a constant volumetric power density (approximately 18 W/m3). These results demonstrate that an MFC design using tubular cathodes coated with nonprecious metal catalysts, and brush anodes, is a promising architecture that is intrinsically scalable for creating larger systems. Further increases in power output will be possible through the development of cathodes with lower internal resistances.     

Duty cycling influences current generation in multi-anode environmental microbial fuel cells

Improving microbial fuel cell (MFC) performance continues to be the subject of research, yet the role of operating conditions, specifically duty cycling, on MFC performance has been modestly addressed. We present a series of studies in which we use a 15-anode environmental MFC to explore how duty cycling (variations in the time an anode is connected) influences cumulative charge, current, and microbial composition. The data reveal particular switching intervals that result in the greatest time-normalized current. When disconnection times are sufficiently short, there is a striking decrease in current due to an increase in the overall electrode reaction resistance. This was observed over a number of whole cell potentials. Based on these results, we posit that replenishment of depleted electron donors within the biofilm and surrounding diffusion layer is necessary for maximum charge transfer, and that proton flux may be not limiting in the highly buffered aqueous phases that are common among environmental MFCs. Surprisingly, microbial diversity analyses found no discernible difference in gross community composition among duty cycling treatments, suggesting that duty cycling itself has little or no effect. Such duty cycling experiments are valuable in determining which factors govern performance of bioelectrochemical systems and might also be used to optimize field-deployed systems.     

Challenges and constraints of using oxygen cathodes in microbial fuel cells

The performance of oxygen reduction catalysts (platinum, pyrolyzed iron(ll) phthalocyanine (pyr-FePc) and cobalt tetramethoxyphenylporphyrin (pyr-CoTMPP)) is discussed in light of their application in microbial fuel cells. It is demonstrated that the physical and chemical environment in microbial fuel cells severely affects the thermodynamics and the kinetics of the electrocatalytic oxygen reduction. The neutral pH in combination with low buffer capacities and low ionic concentrations strongly affect the cathode performance and limit the fuel cell power output. Thus, the limiting current density in galvanodyanamic polarization experiments decreases from 1.5 mA cm(-2) to 0.6 mA cm(-2) (pH 3.3, E(cathode) = 0 V) when the buffer concentration is decreased from 500 to 50 mM. The cathode limitations are superposed by the increasing internal resistance of the MFC that substantially contributes to the decrease of power output. For example, the maximum power output of a model MFC decreased by 35%, from 2.3 to 1.5 mW, whereas the difference between the electrode potentials (deltaE = E(anode) - E(cathode)) decreased only by 10%. The increase of the catalyst load of pyr-FePc from 0.25 to 2 mg cm(-2) increased the cathodic current density from 0.4 to 0.97 mA cm(-2) (pH 7, 50 mM phosphate buffer). The increase of the load of such inexpensive catalyst thus represents a suitable means to improve the cathode performance in microbial fuel cells. Due to the low concentration of protons in MFCs in comparison to relatively high alkali cation levels (ratio C(Na+,K+)/C(H+) = 5 x E5 in pH 7, 50 mM phosphate buffer) the transfer of alkali ions through the proton exchange membrane plays a major role in the charge-balancing ion flux from the anodic into the cathodic compartment. This leads to the formation of pH gradients between the anode and the cathode compartment.     

Cathode performance as a factor in electricity generation in microbial fuel cells

Although microbial fuel cells (MFCs) generate much lower power densities than hydrogen fuel cells, the characteristics of the cathode can also substantially affect electricity generation. Cathodes used for MFCs are often either Pt-coated carbon electrodes immersed in water that use dissolved oxygen as the electron acceptor or they are plain carbon electrodes in a ferricyanide solution. The characteristics and performance of these two cathodes were compared using a two-chambered MFC. Power generation using the Pt-carbon cathode and dissolved oxygen (saturated) reached a maximum of 0.097 mW within 120 h after inoculation (wastewater sludge and 20 mM acetate) when the cathode was equal size to the anode (2.5 x 4.5 cm). Once stable power was generated after replacing the MFC with fresh medium (no sludge), the Coulombic efficiency ranged from 63 to 78%. Power was proportional to the dissolved oxygen concentration in a manner consistent with Monod-type kinetics, with a half saturation constant of K(DO) = 1.74 mg of O2/L. Power increased by 24% when the cathode surface areas were increased from 22.5 to 67.5 cm2 and decreased by 56% when the cathode surface area was reduced to 5.8 cm2. Power was also substantially reduced (by 78% to 0.02 mW) if Pt was not used on the cathode. By using ferricyanide instead of dissolved oxygen, the maximum power increased by 50-80% versus that obtained with dissolved oxygen. This result was primarily due to increased mass transfer efficiencies and the larger cathode potential (332 mV) of ferricyanide than that obtained with dissolved oxygen (268 mV). A cathode potential of 804 mV (NHE basis) is theoretically possible using dissolved oxygen, indicating that further improvements in cathode performance with oxygen as the electron acceptor are possible that could lead to increased power densities in this type of MFC.     

Benchmark and strategy development for microbial fuel cells in industrial wastewater treatment

The chemical energy hidden in wastewater can be extracted, turning an energy-intensive treatment process into an energy-independent one. However, conventional aerobic treat- ment is very energy intensive, and anaerobic treatment requires a post-treatment step to meet stringent discharge requirements. Therefore, Microbial Fuel Cells (MFCs) have attracted a lot of attention because of their ability to extract electrical energy directly from wastewater during the treatment process. Since combustion losses can be avoided, theoretically the greatest energy value can be obtained from the organic load. However, most MFC research is currently still taking place on a laboratory scale in the treatment of synthetic or municipal wastewater. Commercialization of MFC technology will require large-scale plants, for which a suitable MFC design and operation concepts must first be identified, since neither configuration nor operating system has been clearly established yet. In addition, no specific concepts and application fields currently exist for the treat- ment of industrial wastewater. Consequently, with regard to MFCs in industrial wastewater treatment, the aim of this work is to develop a benchmark that serves for modeling the required overall efficiency of MFCs and to identify the most relevant key factors in order to derive enhancement strate- gies. By providing an overview of current MFCs in industrial wastewater treatment and developing a benchmark, the targets for long-term operation of MFCs can be established allowing critical factors for design and operation to be identified. The resulting enhance- ment strategies were validated and the overall evaluation with the developed benchmark allowed an assessment regarding the commercialization potential. Compared to the first MFC design (MFC 1.0), the enhanced MFC design (MFC 2.0) increased the power density by a factor of up to 11 and extended the long-term stability to one year by increasing the specific cathode surface area and reducing the electrode spacing in conjunction with avoiding fiber clogging on the anode side. In addition to using beneficial brewery wastewater with high content of easily degradable organic acids and high conductivity, the performance of the MFC was further stabilized and improved by changing the operating mode to continuous operation and reducing the hydraulic re- tention time to 6 h, resulting in a mean organic removal rate of 6.5 ± 1.9 kg/(m³ · d). Although the overall energy efficiency is low compared to anaerobic treatment, the enor- mous wastewater treatment potential forms the basis for MFCs to become an alternative to conventional treatment technologies if self-sufficient treatment is targeted. Due to the wide range of operating conditions and the modularity of stack systems, MFCs can become a promising option especially for industrial wastewater treatment.     

Characterization of microbial fuel cells at microbially and electrochemically meaningful time scales

The variable biocatalyst density in a microbial fuel cell (MFC) anode biofilm is a unique feature of MFCs relative to other electrochemical systems, yet performance characterizations of MFCs typically involve analyses at electrochemically relevant time scales that are insufficient to account for these variable biocatalyst effects. This study investigated the electrochemical performance and the development of anode biofilm architecture under different external loadings, with duplicate acetate-fed single-chamber MFCs stabilized at each resistance for microbially relevant time scales. Power density curves from these steady-state reactors generally showed comparable profiles despite the fact that anode biofilm architectures and communities varied considerably, showing that steady-state biofilm differences had little influence on electrochemical performance until the steady-state external loading was much larger than the reactor internal resistance. Filamentous bacteria were dominant on the anodes under high external resistances (1000 and 5000 Ω), while more diverse rod-shaped cells formed dense biofilms under lower resistances (10, 50, and 265 Ω). Anode charge transfer resistance decreased with decreasing fixed external resistances, but was consistently 2 orders of magnitude higher than the resistance at the cathode. Cell counting showed an inverse exponential correlation between cell numbers and external resistances. This direct link of MFC anode biofilm evolution with external resistance and electricity production offers several operational strategies for system optimization.     

Substrate-enhanced microbial fuel cells for improved remote power generation from sediment-based systems

A sediment microbial fuel cell (MFC) produces electricity through the bacterial oxidation of organic matter contained in the sediment. The power density is limited, however, due in part to the low organic matter content of most marine sediments. To increase power generation from these devices, particulate substrates were added to the anode compartment. Three materials were tested: two commercially available chitin products differing in particle size and biodegradability (Chitin 20 and Chitin 80) and cellulose powder. Maximum power densities using chitin in this substrate-enhanced sediment MFC (SEM) were 76 +/- 25 and 84 +/- 10 mW/m2 (normalized to cathode projected surface area) for Chitin 20 and Chitin 80, respectively, versus less than 2 mW/m2 for an unamended control. Power generation over a 10 day period averaged 64 +/- 27 mW/ m2 (Chitin 20) and 76 +/- 15 mW/m2 (Chitin 80). With cellulose, a similar maximum power was initially generated (83 +/- 3 mW/m2), but power rapidly decreased after only 20 h. Maximum power densities over the next 5 days varied substantially among replicate cellulose-fed reactors, ranging from 29 +/- 12 to 62 +/- 23 mW/m2. These results suggest a new approach to power generation in remote areas based on the use of particulate substrates. While the longevity of the SEM was relatively short in these studies, it is possible to increase operation times by controlling particle size, mass, and type of material needed to achieve desired power levels that could theoretically be sustained over periods of years or even decades.