Membrane-less cloth cathode assembly (CCA) for scalable microbial fuel cells

One of the main challenges for scaling up microbial fuel cell (MFC) technologies is developing low-cost cathode architectures that can generate high power output. This study developed a simple method to convert non-conductive material (canvas cloth) into an electrically conductive and catalytically active cloth cathode assembly (CCA) in one step. The membrane-less CCA was simply constructed by coating the cloth with conductive paint (nickel-based or graphite-based) and non-precious metal catalyst (MnO₂). Under the fed-batch mode, the tubular air-chamber MFCs equipped with Ni-CCA and graphite-CCA generated the maximum power densities of 86.03 and 24.67 mW m⁻² (normalized to the projected cathode surface area), or 9.87 and 2.83 W m⁻³ (normalized to the reactor liquid volume), respectively. The higher power output of Ni-CCA-MFC was associated with the lower volume resistivity of Ni-CCA (1.35 × 10⁻² Ω cm) than that of graphite-CCA (225 × 10⁻² Ω cm). At an external resistance of 100 Ω, Ni-CCA-MFC and graphite-CCA-MFC removed approximately 95% COD in brewery wastewater within 13 and 18 d, and achieved coulombic efficiencies of 30.2% and 19.5%, respectively. The accumulated net water loss through the cloth by electro-osmotic drag exhibited a linear correlation (R² = 0.999) with produced coulombs. With a comparable power production, such CCAs only cost less than 5% of the previously reported membrane cathode assembly. The new cathode configuration here is a mechanically durable, economical system for MFC scalability.     

A novel configuration of microbial fuel cell stack bridged internally through an extra cation exchange membrane

This paper reports a novel configuration of stacked microbial fuel cells (MFCs) bridged internally through an extra cation exchange membrane (CEM). The MFC stack (MFC_stack), assembled from two single MFCs (MFC_single), resulted in double voltage output and half optimal external resistance. COD removal rate was increased from 32.4% to 54.5%. The performance improvement could be attributed to the smaller internal resistance and enhanced cations transfer. A result from a half cell study further confirmed the important role of the extra CEM. This study also demonstrated MFCs where the anode and cathode were sandwiched between two CEMs possessed significantly high power outputs     

Simultaneous carbon and nitrogen removal using an oxic/anoxic-biocathode microbial fuel cells coupled system

A coupled microbial fuel cell (MFC) system comprising of an oxic-biocathode MFC (O-MFC) and an anoxic-biocathode MFC (A-MFC) was implemented for simultaneous removal of carbon and nitrogen from a synthetic wastewater. The chemical oxygen demand (COD) of the influent was mainly reduced at the anodes of the two MFCs; ammonium was oxidized to nitrate in the O-MFC’s cathode, and nitrate was electrochemically denitrified in the A-MFC’s cathode. The coupled MFC system reached power densities of 14 W/m³ net cathodic compartment (NCC) and 7.2 W/m³ NCC for the O-MFC and the A-MFC, respectively. In addition, the MFC system obtained a maximum COD, NH₄⁺-N and TN removal rate of 98.8%, 97.4% and 97.3%, respectively, at an A-MFC external resistance of 5 Ω, a recirculation ratio (recirculated flow to total influent flow) of 2:1, and an influent flow ratio (O-MFC anode flow to A-MFC anode flow) of 1:1.     

Carbon nanotube supported MnO₂ catalysts for oxygen reduction reaction and their applications in microbial fuel cells

Three types of manganese dioxide, α-MnO(2), β-MnO(2), γ-MnO(2) were tested as alternative cathode catalysts for oxygen reduction reaction (ORR) in air-cathode microbial fuel cells (MFCs). Prepared by solution-based methods, the MnO(2) nanomaterials were comprehensively characterized, and their electrocatalytic activities in neutral electrolyte were investigated with the supporting material of carbon nanotubes (CNTs) by cyclic voltammetry (CV). The CV results showed that all MnO(2) species could catalyze ORR in neutral NaCl solution with different catalytic activities. β-MnO(2) had the highest catalytic activity due to its intrinsic structure and better interaction with CNTs. Three MnO(2) species were further used as cathode catalysts under optimized conditions in air-cathode cubic MFCs, in which mixed culture was inoculated as biocatalysts and domestic wastewater was used as the substrate in the anode chamber. It was also found that β-MnO(2) based MFC yielded the best performance with a power density of 97.8 mWm(-2) which was 64.1% that of the Pt-based MFC, and a lower internal resistance of 165 Ω. Furthermore, the COD removal efficiency of β-MnO(2) based MFC was estimated as 84.8%, higher than that of the Pt-based MFC. This study demonstrated that using β-MnO(2) on CNT support instead of Pt could potentially improve the feasibility of scaling up air-cathode MFCs for practical applications by lowering the material cost.     

Increased sustainable electricity generation in up-flow air-cathode microbial fuel cells

Sustainable electricity was generated from glucose in up-flow air-cathode microbial fuel cells (MFCs) with carbon cloth cathode and carbon granular anode. Plastic sieves rather than membrane were used to separate the anode and cathode. Based on 1g/l glucose as substrate, a maximum volumetric power density of 25+/-4 W/m(3) (89 A/m(3)) was obtained for the MFC with a sieve area of 30 cm(2) and 49+/-3 W/m(3) (215 A/m(3)) for the MFC with a sieve area of 60 cm(2). The increased power density with larger sieve area was mainly due to the decrease of internal resistance according to the electrochemistry impedance spectroscopy analysis. Increasing the sieve area from 30 cm(2) to 60 cm(2) resulted in a decrease of overall internal resistance from 41 ohm to 27.5 ohm and a decrease of ohmic resistance from 24.3 ohm to 14 ohm. While increasing operational recirculation ratio (RR) decreased internal resistance and increased power output at low substrate concentration, the effect of RR on cell performance was negligible at higher substrate concentration.     

Performance and microbial ecology of air-cathode microbial fuel cells with layered electrode assemblies

Microbial fuel cells (MFCs) can be built with layered electrode assemblies, where the anode, proton exchange membrane (PEM), and cathode are pressed into a single unit. We studied the performance and microbial community structure of MFCs with layered assemblies, addressing the effect of materials and oxygen crossover on the community structure. Four MFCs with layered assemblies were constructed using Nafion or Ultrex PEMs and a plain carbon cloth electrode or a cathode with an oxygen-resistant polytetrafluoroethylene diffusion layer. The MFC with Nafion PEM and cathode diffusion layer achieved the highest power density, 381 mW/m² (20 W/m³). The rates of oxygen diffusion from cathode to anode were three times higher in the MFCs with plain cathodes compared to those with diffusion-layer cathodes. Microsensor studies revealed little accumulation of oxygen within the anode cloth. However, the abundance of bacteria known to use oxygen as an electron acceptor, but not known to have exoelectrogenic activity, was greater in MFCs with plain cathodes. The MFCs with diffusion-layer cathodes had high abundance of exoelectrogenic bacteria within the genus Geobacter. This work suggests that cathode materials can significantly influence oxygen crossover and the relative abundance of exoelectrogenic bacteria on the anode, while PEM materials have little influence on anode community structure. Our results show that oxygen crossover can significantly decrease the performance of air-cathode MFCs with layered assemblies, and therefore limiting crossover may be of particular importance for these types of MFCs.     

Effects of sulfide on microbial fuel cells with platinum and nitrogen-doped carbon powder cathodes

Because of the advantages of low cost, good electrical conductivity and high oxidation resistance, nitrogen-doped carbon (NDC) materials have a potential to replace noble metals in microbial fuel cells (MFCs) for wastewater treatment. In spite of a large volume of studies on NDC materials as catalysts for oxygen reduction reaction, the influence of sulfide on NDC materials has not yet been explicitly reported so far. In this communication, nitrogen-doped carbon powders (NDCP) were prepared by treating carbon powders in nitric acid under reflux condition. Sodium sulfide (Na(2)S) was added to the cathodic electrolyte to compare its effects on platinum (Pt) and NDCP cathodes. Cell voltages, power density and cathodic potentials were monitored without and with Na(2)S and after Na(2)S was removed. The maximum cell voltage of the MFCs with Pt cathode decreased by 10% in the presence of Na(2)S that did not change the performance of the MFC with NDCP cathode, and the maximum power density of the MFC with NDCP cathode was even 11.3% higher than that with Pt cathode (222.5 ± 8 mW m(-2) vs. 199.7 ± 4 mW m(-2)).     

Power generation using spinel manganese-cobalt oxide as a cathode catalyst for microbial fuel cell applications

This study focused on the use of spinel manganese-cobalt (Mn-Co) oxide, prepared by a solid state reaction, as a cathode catalyst to replace platinum in microbial fuel cells (MFCs) applications. Spinel Mn-Co oxides, with an Mn/Co atomic ratios of 0.5, 1, and 2, were prepared and examined in an air cathode MFCs which was fed with a molasses-laden synthetic wastewater and operated in batch mode. Among the three Mn-Co oxide cathodes and after 300 h of operation, the Mn-Co oxide catalyst with Mn/Co atomic ratio of 2 (MnCo-2) exhibited the highest power generation 113 mW/m2 at cell potential of 279 mV, which were lower than those for the Pt catalyst (148 mW/m2 and 325 mV, respectively). This study indicated that using spinel Mn-Co oxide to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs.     

Layer-by-layer construction of graphene-based microbial fuel cell for improved power generation and methyl orange removal

Development of highly efficient anode is critical for enhancing the power output of microbial fuel cells (MFCs). The aim of this work is to investigate whether modification of carbon paper (CP) anode with graphene (GR) via layer-by-layer assembly technique is an effective approach to promote the electricity generation and methyl orange removal in MFCs. Using cyclic voltammetry and electrochemical impedance spectroscopy, the GR/CP electrode exhibited better electrochemical behavior. Scanning electron microscopy results revealed that the surface roughness of GR/CP increased, which was favorable for more bacteria to attach to the anode surface. The MFCs equipped with GR/CP anode achieved a stable maximum power density of 368 mW m^?2 under 1,000 Ω external resistance and a start time for the initial maximum voltage of 180 h, which were, respectively, 51 % higher and 31 % shorter than the corresponding values of the MFCs with blank anode. The anode and cathode polarization curves revealed negligible difference in cathode potentials but obviously difference in anode potentials, indicating that the GR-modified anode other than the cathode was responsible for the performance improvement of MFC. Meanwhile, compared with MFCs with blank anode, 11 % higher decolorization efficiency and 16 % higher the chemical oxygen demand removal rate were achieved in MFC with GR-modified anode during electricity generation. This study might provide an effective way to modify the anode for enhanced electricity generation and efficient removal of azo dye in MFCs.     

Assessment of organic removal in series- and parallel-connected microbial fuel cell stacks

Microbial fuel cells (MFCs) degrade organic contaminants in wastewater while simultaneously producing electricity, but must be stacked to yield adequate voltage and current. This study examined the evolution of the chemical oxygen demand (COD) removal rate and efficiency in two identical individual MFCs (i-MFCs) in series- and parallel-connected stacks (sc- and pc-MFCs, respectively) under batch and continuous operation. The stack voltage and current increased in the respective series and parallel connections of the two i-MFCs (MFC unit 1 and MFC unit 2). Voltage reversal was observed in the sc- MFC below an external load of 100 Ω. Regardless of occurrence of the voltage reversal, organic reduction between i-MFCs and sc-MFCs showed no significant difference (gap of < 9% and < 6% in COD removal rate and efficiency, respectively); additionally, organic removals between the two individual MFCs in series indicated differences less than 9% of COD removal rate and 5% of COD removal efficiency in batch mode. Continuous operation also yielded similar organic removals as the MFCs in individual and series connection (voltage reversal occurred) mode, even over 8 days operation. Parallel connection yielded identical organic removals and currents in the two individual MFCs of the pc-MFC, even though the two separate i-MFCs showed different organic removal rates and current productions. This study provides the guide for the application of stacked MFCs for power source and efficient organic pollutant removal in wastewater treatment process.     

Flexible and Stretchable Biobatteries: Monolithic Integration of Membrane‐Free Microbial Fuel Cells in a Single Textile Layer

The fabrication and performance of a flexible and stretchable microbial fuel cell (MFC) monolithically integrated into a single sheet of textile substrate are reported. The single‐layer textile MFC uses Pseudomonas aeruginosa (PAO1) as a biocatalyst to produce a maximum power of 6.4 µW cm^?2 and current density of 52 µA cm^?2, which are substantially higher than previous textile‐MFCs and are similar to other flexible paper‐based MFCs. The textile MFC demonstrates a stable performance with repeated stretching and twisting cycles. The membrane‐less single‐chamber configuration drastically simplifies the fabrication and improves the performance of the MFC. A conductive and hydrophilic anode in a 3D fabric microchamber maximizes bacterial electricity generation from a liquid environment and a silver oxide/silver solid‐state cathode reduces cathodic overpotential for fast catalytic reaction. A simple batch fabrication approach simultaneously constructs 35 individual devices, which will revolutionize the mass production of textile MFCs. This stretchable and twistable power device printed directly onto a single textile substrate can establish a standardized platform for textile‐based biobatteries and will be potentially integrated into wearable electronics in the future.     

Simultaneous degradation of refractory contaminants in both the anode and cathode chambers of the microbial fuel cell

In this study, the microbial fuel cell (MFC) was combined with the Fenton-like technology to simultaneously generate electricity and degrade refractory contaminants in both anode and cathode chambers. The maximum power density achieved was 15.9 W/m³ at an initial pH of 3.0 in the MFC. In the anode chamber, approximately 100% of furfural and 96% COD were removed at the end of a cycle. In the cathode chamber, the Fenton-like reaction with FeVO₄ as a catalyst enhanced the removal of AO7 and COD. The removal rates of AO7 and COD reached 89% and 81%, respectively. The optimal pH value and FeVO₄ dosage toward degrading AO7 were about 3.0 and 0.8 g, respectively. Furthermore, a two-way catalyst mechanism of FeVO₄ and the contaminant degradation pathway in the MFC were explored.     

A multi-electrode continuous flow microbial fuel cell with separator electrode assembly design

Scaling up microbial fuel cells (MFCs) requires the development of compact reactors with multiple electrodes. A scalable single chamber MFC (130 mL), with multiple graphite fiber brush anodes and a single air-cathode cathode chamber (27 m²/m³), was designed with a separator electrode assembly (SEA) to minimize electrode spacing. The maximum voltage produced in fed-batch operation was 0.65 V (1,000 Ω) with a textile separator, compared to only 0.18 V with a glass fiber separator due to short-circuiting by anode bristles through this separator with the cathode. The maximum power density was 975 mW/m², with an overall chemical oxygen demand (COD) removal of >90% and a maximum coulombic efficiency (CE) of 53% (50 Ω resistor). When the reactor was switched to continuous flow operation at a hydraulic retention time (HRT) of 8 h, the cell voltage was 0.21 ± 0.04 V, with a very high CE = 85%. Voltage was reduced to 0.13 ± 0.03 V at a longer HRT = 16 h due to a lower average COD concentration, and the CE (80%) decreased slightly with increased oxygen intrusion into the reactor per amount of COD removed. Total internal resistance was 33 Ω, with a solution resistance of 2 Ω. These results show that the SEA type MFC can produce stable power and a high CE, making it useful for future continuous flow treatment using actual wastewaters.     

Fabrication of stainless steel mesh gas diffusion electrode for power generation in microbial fuel cell

This study reports the fabrication of a new membrane electrode assembly by using stainless steel mesh (SSM) as raw material and its effectiveness as gas diffusion electrode (GDE) for electrochemical oxygen reduction in microbial fuel cell (MFC). Based on feeding glucose (0.5 g L(-1)) substrate to a single-chambered MFC, power generation using SSM-based GDE was increased with the decrease of polytetrafluoroethylene (PTFE) content applied during fabrication, reaching the optimum power density of 951.6 mW m(-2) at 20% PTFE. Repeatable cell voltage of 0.51 V (external resistance of 400 Ω) and maximum power density of 951.6 mW m(-2) produced for the MFC with SSM-based GDE are comparable to that of 0.52 V and 972.6 mW m(-2), respectively obtained for the MFC containing typical carbon cloth (CC)-made GDE. Besides, Coulombic efficiency (CE) is found higher for GDE (SSM or CC) with membrane assembly than without, which results preliminarily from the mitigation of Coulombic loss being associated with oxygen diffusion and substrate crossover. This study demonstrates that with its good electrical conductivity and much lower cost, the SSM-made GDE suggests a promising alternative as efficient and more economically viable material to conventional typical carbon for power production from biomass in MFC.     

Air-cathode structure optimization in separator-coupled microbial fuel cells

Microbial fuel cells (MFC) with 30% wet-proofed air cathodes have previously been optimized to have 4 diffusion layers (DLs) in order to limit oxygen transfer into the anode chamber and optimize performance. Newer MFC designs that allow close electrode spacing have a separator that can also reduce oxygen transfer into the anode chamber, and there are many types of carbon wet-proofed materials available. Additional analysis of conditions that optimize performance is therefore needed for separator-coupled MFCs in terms of the number of DLs and the percent of wet proofing used for the cathode. The number of DLs on a 50% wet-proofed carbon cloth cathode significantly affected MFC performance, with the maximum power density decreasing from 1427 to 855 mW/m² for 1–4 DLs. A commonly used cathode (30% wet-proofed, 4 DLs) produced a maximum power density (988 mW/m²) that was 31% less than that produced by the 50% wet-proofed cathode (1 DL). It was shown that the cathode performance with different materials and numbers of DLs was directly related to conditions that increased oxygen transfer. The coulombic efficiency (CE) was more affected by the current density than the oxygen transfer coefficient for the cathode. MFCs with the 50% wet-proofed cathode (2 DLs) had a CE of >84% (6.8 A/m²), which was substantially larger than that previously obtained using carbon cloth air-cathodes lacking separators. These results demonstrate that MFCs constructed with separators should have the minimum number of DLs that prevent water leakage and maximize oxygen transfer to the cathode.     

Enhanced nitrogen removal in single‐chamber microbial fuel cells with increased gas diffusion areas

Single‐chamber microbial fuel cells (MFCs) with nitrifiers pre‐enriched at the air cathodes have previously been demonstrated as a passive strategy for integrating nitrogen removal into current‐generating bioelectrochemical systems. To further define system design parameters for this strategy, we investigated in this study the effects of oxygen diffusion area and COD/N ratio in continuous‐flow reactors. Doubling the gas diffusion area by adding an additional air cathode or a diffusion cloth significantly increased the ammonia and COD removal rates (by up to 115% and 39%), ammonia removal efficiency (by up to 134%), the cell voltage and cathode potentials, and the power densities (by a factor of approximately 2). When the COD/N ratio was lowered from 13 to 3, we found up to 244% higher ammonia removal rate but at least 19% lower ammonia removal efficiency. An increase of COD removal rate by up to 27% was also found when the COD/N ratio was lowered from 11 to 3. The Coulombic efficiency was not affected by the additional air cathode, but decreased by an average of 11% with the addition of a diffusion cloth. Ammonia removal by assimilation was also estimated to understand the ammonia removal mechanism in these systems. These results showed that the doubling of gas diffusion area enhanced N and COD removal rates without compromising electrochemical performance. Biotechnol. Bioeng. 2013; 110: 785–791. © 2012 Wiley Periodicals, Inc.     

Evaluation of hydrolysis and fermentation rates in microbial fuel cells

This study determined the influence of substrate degradation on power generation in microbial fuel cells (MFCs) and microbial community selection on the anode. Air cathode MFCs were fed synthetic medium containing different substrates (acetate, glucose and starch) using primary clarifier sewage as source of electroactive bacteria. The complexity of the substrate affected the MFC performance both for power generation and COD removal. Power output decreased with an increase in substrate complexity from 99 ± 2 mW m⁻² for acetate to 4 ± 2 mW m⁻² for starch. The organic matter removal and coulombic efficiency (CE) of MFCs with acetate and glucose (82% of COD removal and 26% CE) were greater than MFCs using starch (60% of COD removal and 19% of CE). The combined hydrolysis–fermentation rate obtained (0.0024 h⁻¹) was considerably lower than the fermentation rate (0.018 h⁻¹), indicating that hydrolysis of complex compounds limits current output over fermentation. Statistical analysis of microbial community fingerprints, developed on the anode, showed that microbial communities were enriched according to the type of substrate used. Microbial communities producing high power outputs (fed acetate) clustered separately from bacterial communities producing low power outputs (fed complex compounds).     

Microfiltration membrane performance in two-chamber microbial fuel cells

Proton exchange membranes (PEMs) are typically used in two-chamber microbial fuel cells (MFCs) to separate the anode and cathode chambers while allowing protons to pass between the chambers. However, PEMs such as Nafion are not cost-effective. To reduce the cost of MFCs, we examined the performances of cellulose acetate microfiltration membranes in a two-chamber microbial fuel cell using acetate. The internal resistance, the maximum power density and the coulombic efficiency (CE) of the microfiltration membrane MFC (MMMFC) were 263 Ω, 0.831 ± 0.016 W/m² and 38.5 ± 3.5%, respectively, in a fed-batch mode, while the corresponding values of the MFC using a PEM were 267 Ω, 0.872 ± 0.021 W/m² and 74.7 ± 4.6%, respectively. We further used the MMMFC for poultry wastewater treatment. The maximum power density of 0.746 ± 0.024 W/m² and CE of 35.3 ± 3.2% were achieved when the poultry wastewater containing 566 mg/L COD was used, removing 81.6 ± 6.6% of the COD. These results demonstrate microfiltration membranes, compared with PEMs, have a similar internal resistance and reduce pH gradient across the membrane. They parallel PEMs in maximum power density, while CE is much lower due to the oxygen and substrate diffusion. The MMMFC was effective for poultry wastewater treatment with high COD removal.     

Electricity generation from real industrial wastewater using a single-chamber air cathode microbial fuel cell with an activated carbon anode

This study introduces activated carbon (AC) as an effective anode for microbial fuel cells (MFCs) using real industrial wastewater without treatment or addition of external microorganism mediators. Inexpensive activated carbon is introduced as a proper electrode alternative to carbon cloth and carbon paper materials, which are considered too expensive for the large-scale application of MFCs. AC has a porous interconnected structure with a high bio-available surface area. The large surface area, in addition to the high macro porosity, facilitates the high performance by reducing electron transfer resistance. Extensive characterization, including surface morphology, material chemistry, surface area, mechanical strength and biofilm adhesion, was conducted to confirm the effectiveness of the AC material as an anode in MFCs. The electrochemical performance of AC was also compared to other anodes, i.e., Teflon-treated carbon cloth (CCT), Teflon-treated carbon paper (CPT), untreated carbon cloth (CC) and untreated carbon paper (CP). Initial tests of a single air-cathode MFC display a current density of 1792 mAm⁻², which is approximately four times greater than the maximum value of the other anode materials. COD analyses and Coulombic efficiency (CE) measurements for AC-MFC show the greatest removal of organic compounds and the highest CE efficiency (60 and 71%, respectively). Overall, this study shows a new economical technique for power generation from real industrial wastewater with no treatment and using inexpensive electrode materials.

     

Composition and distribution of internal resistance in three types of microbial fuel cells

High internal resistance is a key problem limiting the power output of the microbial fuel cell (MFC). Therefore, more knowledge about the internal resistance is essential to enhance the performance of the MFC. However, different methods are used to determine the internal resistance, which makes the comparison difficult. In this study, three different types of MFCs were constructed to study the composition and distribution of internal resistance. The internal resistance (R _i) is partitioned into anodic resistance (R _a), cathodic resistance (R _c), and ohmic resistance () according to their origin and the design of the MFCs. These three resistances were then evaluated by the “current interrupt” method and the “steady discharging” method based on the proposed equivalent circuits for MFCs. In MFC-A, MFC-B, and MFC-C, the R _i values were 3.17, 0.35, and 0.076 Ω m², the values were 2.65, 0.085, and 0.008 Ω m², the R _a values were 0.055, 0.115, and 0.034 Ω m², and the R _c values were 0.466, 0.15, and 0.033 Ω m², respectively. For MFC-B and MFC-C, the remarkable decrease in R _i compared with the two-chamber MFC was mainly ascribed to the decline in and R _c. In MFC-C, the membrane electrodes’ assembly lowered the ohmic resistance and facilitated the mass transport through the anode and cathode electrodes, resulting in the lowest R _i among the three types.