Recycled tire crumb rubber anodes for sustainable power production in microbial fuel cells

One of the greatest challenges facing microbial fuel cells (MFCs) in large scale applications is the high cost of electrode material. We demonstrate here that recycled tire crumb rubber coated with graphite paint can be used instead of fine carbon materials as the MFC anode. The tire particles showed satisfactory conductivity after 2-4 layers of coating. The specific surface area of the coated rubber was over an order of magnitude greater than similar sized graphite granules. Power production in single chamber tire-anode air-cathode MFCs reached a maximum power density of 421 mW m⁻², with a coulombic efficiency (CE) of 25.1%. The control graphite granule MFC achieved higher power density (528 mW m⁻²) but lower CE (15.6%). The light weight of tire particle could reduce clogging and maintenance cost but posts challenges in conductive connection. The use of recycled material as the MFC anodes brings a new perspective to MFC design and application and carries significant economic and environmental benefit potentials.     

Treatment of carbon fiber brush anodes for improving power generation in air-cathode microbial fuel cells

Carbon brush electrodes have been used to provide high surface areas for bacterial growth and high power densities in microbial fuel cells (MFCs). A high-temperature ammonia gas treatment has been used to enhance power generation, but less energy-intensive methods are needed for treating these electrodes in practice. Three different treatment methods are examined here for enhancing power generation of carbon fiber brushes: acid soaking (CF-A), heating (CF-H), and a combination of both processes (CF-AH). The combined heat and acid treatment improve power production to 1370 mW m⁻², which is 34% larger than the untreated control (CF-C, 1020 mW m⁻²). This power density is 25% higher than using only acid treatment (1100 mW m⁻²) and 7% higher than that using only heat treatment (1280 mW m⁻²). XPS analysis of the treated and untreated anode materials indicates that power increases are related to higher N1s/C1s ratios and a lower C-O composition. These findings demonstrate efficient and simple methods for improving power generation using graphite fiber brushes, and provide insight into reasons for improving performance that may help to further increase power through other graphite fiber modifications.     

Carbon nanotube modified air-cathodes for electricity production in microbial fuel cells

The use of air-cathodes in microbial fuel cells (MFCs) has been considered sustainable for large scale applications, but the performance of most current designs is limited by the low efficiency of the three-phase oxygen reduction on the cathode surface. In this study we developed carbon nanotube (CNT) modified air-cathodes to create a 3-D electrode network for increasing surface area, supporting more efficient catalytic reaction, and reducing the kinetic resistance. Compared with traditional carbon cloth cathodes, all nanotube modified cathodes showed higher performance in electrochemical response and power generation in MFCs. Reactors using carbon nanotube mat cathodes showed the maximum power density of 329 mW m⁻²; more than twice that of the peak power obtained with carbon cloth cathodes (151 mW m⁻²). The addition of Pt catalysts significantly increased the current densities of all cathodes, with the maximum power density obtained using the Pt/carbon nanotube mat cathode at 1118 mW m⁻². The stable maximum power density obtained from other nanotube coated cathodes varied from 174 mW m⁻² to 522 mW m⁻². Scanning electron micrographs showed the presence of conductive carbon nanotube networks on the CNT modified cathodes that provide more efficient oxygen reduction.     

Performance of two different types of anodes in membrane electrode assembly microbial fuel cells for power generation from domestic wastewater

Graphite fiber brush electrodes provide high surface areas for exoelectrogenic bacteria in microbial fuel cells (MFCs), but the cylindrical brush format limits more compact reactor designs. To enable MFC designs with closer electrode spacing, brush anodes were pressed up against a separator (placed between the electrodes) to reduce the volume occupied by the brush. Higher maximum voltages were produced using domestic wastewater (COD = 390 ± 89 mg L⁻¹) with brush anodes (360 ± 63 mV, 1000 Ω) than woven carbon mesh anodes (200 ± 81 mV) with one or two separators. Maximum power densities were similar for brush anode reactors with one or two separators after 30 days (220 ± 1.2 and 240 ± 22 mW m⁻²), but with one separator the brush anode MFC power decreased to 130 ± 55 mW m⁻² after 114 days. Power densities in MFCs with mesh anodes were very low (<45 mW m⁻²). Brush anodes MFCs had higher COD removals (80 ± 3%) than carbon mesh MFCs (58 ± 7%), but similar Coulombic efficiencies (8.6 ± 2.9% brush; 7.8 ± 7.1% mesh). These results show that compact (hemispherical) brush anodes can produce higher power and more effective domestic wastewater treatment than flat mesh anodes in MFCs.     

Flame synthesis of carbon nanostructures on stainless steel anodes for use in microbial fuel cells

Microbial fuel cells (MFCs) offer a promising alternative energy technology, but suffer from low power densities which hinder their practical applicability. In order to improve anodic power density, we deposited carbon nanostructures (CNSs) on an otherwise plain stainless steel mesh (SS-M) anode. Using a flame synthesis method that did not require pretreatment of SS-M substrates, we were able to produce these novel CNS-enhanced SS-M (CNS-M) anodes quickly (in a matter of minutes) and inexpensively, without the added costs of chemical pretreatments. During fed batch experiments with biomass from anaerobic digesters in single-chamber MFCs, the median power densities (based on the projected anodic surface area) were 2.9 mW m⁻² and 187 mW m⁻² for MFCs with SS-M and CNS-M anodes, respectively. The addition of CNSs to a plain SS-M anode via flame deposition therefore resulted in a 60-fold increase in the median power production. The combination of CNSs and metallic current collectors holds considerable promise for power production in MFCs.     

Polypyrrole/carbon black composite as a novel oxygen reduction catalyst for microbial fuel cells

A polypyrrole/carbon black (Ppy/C) composite has been employed as an electrocatalyst for the oxygen reduction reaction (ORR) in an air-cathode microbial fuel cell (MFC). The electrocatalytic activity of the Ppy/C is evaluated toward the oxygen reduction using cyclic voltammogram and linear sweep voltammogram methods. In comparison with that at the carbon black electrode, the peak potential of the ORR at the Pp/C electrode shifts by approximate 260 mV towards positive potential, demonstrating the electrocatalytic activity of Ppy toward ORR. Additionally, the results of the MFC experiments show that the Ppy/C is well suitable to fully substitute the traditional cathode materials in MFCs. The maximum power density of 401.8 mW m⁻² obtained from the MFC with a Ppy/C cathode is higher than that of 90.9 mW m⁻² with a carbon black cathode and 336.6 mW m⁻² with a non-pyrolysed FePc cathode. Although the power output with a Ppy/C cathode is lower than that with a commercial Pt cathode, the power per cost of a Ppy/C cathode is 15 times greater than that of a Pt cathode. Thus, the Ppy/C can be a good alternative to Pt in MFCs due to the economic advantage.     

Polymer coatings as separator layers for microbial fuel cell cathodes

Membrane separators reduce oxygen flux from the cathode into the anolyte in microbial fuel cells (MFCs), but water accumulation and pH gradients between the separator and cathode reduces performance. Air cathodes were spray-coated (water-facing side) with anion exchange, cation exchange, and neutral polymer coatings of different thicknesses to incorporate the separator into the cathode. The anion exchange polymer coating resulted in greater power density (1167 ± 135 mW m⁻²) than a cation exchange coating (439 ± 2 mW m⁻²). This power output was similar to that produced by a Nafion-coated cathode (1114 ± 174 mW m⁻²), and slightly lower than the uncoated cathode (1384 ± 82 mW m⁻²). Thicker coatings reduced oxygen diffusion into the electrolyte and increased coulombic efficiency (CE = 56-64%) relative to an uncoated cathode (29 ± 8%), but decreased power production (255-574 mW m⁻²). Electrochemical characterization of the cathodes ex situ to the MFC showed that the cathodes with the lowest charge transfer resistance and the highest oxygen reduction activity produced the most power in MFC tests. The results on hydrophilic cathode separator layers revealed a trade off between power and CE. Cathodes coated with a thin coating of anion exchange polymer show promise for controlling oxygen transfer while minimally affecting power production.     

Polyaniline/carbon black composite-supported iron phthalocyanine as an oxygen reduction catalyst for microbial fuel cells

Polyaniline/carbon black (PANI/C) composite-supported iron phthalocyanine (FePc) (PANI/C/FePc) has been investigated as a catalyst for the oxygen reduction reaction (ORR) in an air-cathode microbial fuel cell (MFC). The electrocatalytic activity of the PANI/C/FePc toward the ORR is evaluated using cyclic voltammogram and linear scan voltammogram methods. In comparison with that of carbon-supported FePc electrode, the peak potential of the ORR at the PANI/C/FePc electrode shifts toward positive potential, and the peak current is greatly increased, suggesting the enhanced activity of FePc absorbed onto PANI/C. Additionally, the results of the MFC experiments show that PANI/C/FePc is well suitable to be the cathode material for MFCs. The maximum power density of 630.5 mW m⁻² with the PANI/C/FePc cathode is higher than that of 336.6 mW m⁻² with the C/FePc cathode, and even higher that that of 575.6 mW m⁻² with a Pt cathode. Meanwhile, the power per cost of the PANI/C/FePc cathode is 7.5 times greater than that of the Pt cathode. Thus, the PANI/C/FePc can be a potential alternative to Pt in MFCs.     

Electricity generation by a baffle-chamber membraneless microbial fuel cell

Microbial fuel cells (MFCs) for organic waste and wastewater treatment represent innovative technologies for pollution control and energy generation. The research reported here considers the influence of reactor configurations designed to mitigate the impact of oxygen transport on electricity generation by a baffle-chamber membraneless MFC. The reactor was constructed to reduce mixing in the vicinity of the cathode and facilitate thick (>1 mm) biofilm formation on the cathode by adding anaerobic biomass/sludge (4330 ± 410 mg COD L⁻¹), resulting in an overall coulombic efficiency of more than 30% at glucose concentrations ranging from 96 to 960 mg COD L⁻¹, compared to previously reported efficiencies <10% in a completely mixed membraneless MFC. Efficiencies in the absence of anaerobic sludge dropped to 21.2 ± 3.7%, suggesting that the importance of pH buffering provided by the biomass in improving electron transport to the anode. However, the anaerobic sludge itself provided very limited power (approximately 0.3 mW m⁻²) and power generation was primarily associated with glucose degradation (e.g., 129 ± 15 mW m⁻²).     

Ammonia inhibition of electricity generation in single-chambered microbial fuel cells

Batch experiments are conducted at various concentrations of initial total ammonia nitrogen (TAN) with acetate as an electron donor to examine the effects of free ammonia (NH₃) inhibition on electricity production in single-chambered microbial fuel cells (MFCs). This research demonstrates that initial TAN concentrations of over 500 mg N L⁻¹ significantly inhibit electricity generation in MFCs. The maximum power density of 4240 mW m⁻³ at 500 mg N L⁻¹ drastically decreases to 1700 mW m⁻³ as the initial TAN increases up to 4000 mg N L⁻¹. Nitrite and nitrate analysis confirms that nitrification after complete acetate removal consumes some TAN. Ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB) are also inhibited by increasing the initial TAN concentrations. Another batch experiment verifies the strong inhibitory effect of TAN with only small differences between the half-maximum effective concentration (EC₅₀) for TAN (894 mg N L⁻¹ equivalent to 10 mg N L⁻¹ as NH₃) and optimum TAN conditions; it requires careful monitoring of the TAN for MFCs. In addition, abiotic control experiments reveal that granular activated carbon, which is used as an auxiliary anode material, adsorbs a significant amount of ammonia at each TAN concentration in batch MFCs.     

Power generation using carbon mesh cathodes with different diffusion layers in microbial fuel cells

An inexpensive carbon material, carbon mesh, was examined to replace the more expensive carbon cloth usually used to make cathodes in air-cathode microbial fuel cells (MFCs). Three different diffusion layers were tested using carbon mesh: poly(dimethylsiloxane) (PDMS), polytetrafluoroethylene (PTFE), and Goretex cloth. Carbon mesh with a mixture of PDMS and carbon black as a diffusion layer produced a maximum power density of 1355 ± 62 mW m⁻² (normalized to the projected cathode area), which was similar to that obtained with a carbon cloth cathode (1390 ± 72 mW m⁻²). Carbon mesh with a PTFE diffusion layer produced only a slightly lower (6.6%) maximum power density (1303 ± 48 mW m⁻²). The Coulombic efficiencies were a function of current density, with the highest value for the carbon mesh and PDMS (79%) larger than that for carbon cloth (63%). The cost of the carbon mesh cathode with PDMS/Carbon or PTFE (excluding catalyst and binder costs) is only 2.5% of the cost of the carbon cloth cathode. These results show that low cost carbon materials such as carbon mesh can be used as the cathode in an MFC without reducing the performance compared to more expensive carbon cloth.     

Generation of electricity in microbial fuel cells at sub-ambient temperatures

Direct generation of electricity from a mixture of carbon sources was examined using single chamber mediator-less air cathode microbial fuel cells (MFCs) at sub-ambient temperatures. Electricity was directly generated from a carbon source mixture of d-glucose, d-galactose, d-xylose, d-glucuronic acid and sodium acetate at 30 °C and <20 °C (down to 4 °C). Anodic biofilms enriched at different temperatures using carbon source mixtures were examined using epi-fluorescent, scanning electron microscopy, and cyclic voltammetry for electrochemical evaluation. The maximum power density obtained at different temperatures ranged from 486 ± 68 mW m⁻² to 602 ± 38 mW m⁻² at current density range of 0.31 mA cm⁻² to 0.41 mA cm⁻² (14 °C and 30 °C, respectively). Coulombic efficiency increased with decreasing temperature, and ranged from 24 ± 3 to 38 ± 1% (20 °C and 4 °C, respectively). Chemical oxygen demand (COD) removal was over 68% for all carbon sources tested. Our results demonstrate adaptation, by gradual increase of cold-stress, to electricity production in MFCs at sub-ambient temperatures.     

Integrating engineering design improvements with exoelectrogen enrichment process to increase power output from microbial fuel cells

Microbial fuel cells (MFC) hold promise as a green technology for bioenergy production. The challenge is to improve the engineering design while exploiting the ability of microbes to generate and transfer electrons directly to electrodes. A strategy using a combination of improved anode design and an enrichment process was formulated to improve power densities. The design was based on a flow-through anode with minimal dead volume and a high electrode surface area per unit volume. The strategy focused on promoting biofilm formation via a combination of forced flow through the anode, carbon limitation, and step-wise reduction of external resistance. The enrichment process resulted in development of exoelectrogenic biofilm communities dominated by Anaeromusa spp. This is the first report identifying organisms from the Veillonellaceae family in MFCs. The power density of the resulting MFC using a ferricyanide cathode reached 300 W m⁻³ net anode volume (3220 mW m⁻²), which is about a third of what is estimated to be necessary for commercial consideration. The operational stability of the MFC using high specific surface area electrodes was demonstrated by operating the MFC for a period of over four months.     

Enhanced Coulombic efficiency and power density of air-cathode microbial fuel cells with an improved cell configuration

Single chamber air-cathode microbial fuel cells (MFCs) that lack a proton exchange membrane (PEM) hold a great promise for many practical applications due to their low operational cost, simple configuration and relative high power density. One of the great challenges for PEM-less MFC is that the Coulombic efficiency is much lower than those containing PEM. In this study, single-chamber PEM-less MFCs were adapted by applying a J-Cloth layer on the water-facing side of air cathode. Due to the significant reduction of oxygen diffusion by the J-Cloth, the MFCs with two-layers of J-Cloth demonstrated an over 100% increase in Coulombic efficiency in comparison with those without J-Cloth (71% versus 35%) at the same current density of 0.6 mA cm⁻². A new cell configuration, cloth electrode assembly (CEA), therefore, was designed by sandwiching the cloth between the anode and the cathode. Such an MFC configuration greatly reduced the internal resistance, resulting in a power density of 627 W m⁻³ when operated in fed-batch mode and 1010 W m⁻³ in continuous-flow mode, which is the highest reported power density for MFCs and more than 15 times higher than those reported for air-cathode MFCs using similar electrode materials. This study indicates that the Coulombic efficiency and power density of air-cathode MFCs can be improved significantly using an inexpensive cloth layer, which greatly increases the feasibility for the practical applications of MFCs.     

A thermophilic microbial fuel cell design

Microbial fuel cells (MFCs) are reactors able to generate electricity by capturing electrons from the anaerobic respiratory processes of microorganisms. While the majority of MFCs have been tested at ambient or mesophilic temperatures, thermophilic systems warrant evaluation because of the potential for increased microbial activity rates on the anode. MFC studies at elevated temperatures have been scattered, using designs that are already established, specifically air-cathode single chambers and two-chamber designs. This study was prompted by our previous attempts that showed an increased amount of evaporation in thermophilic MFCs, adding unnecessary technical difficulties and causing excessive maintenance. In this paper, we describe a thermophilic MFC design that prevents evaporation. The design was tested at 57 °C with an anaerobic, thermophilic consortium that respired with glucose to generate a power density of 375 mW m⁻² after 590 h. Polarization and voltage data showed that the design works in the batch mode but the design allows for adoption to continuous operation.     

Microbial fuel cell performance with non-Pt cathode catalysts

Various cathode catalysts prepared from metal porphyrines and phthalocyanines were examined for their oxygen reduction activity in neutral pH media. Electrochemical studies were carried out with metal tetramethoxyphenylporphyrin (TMPP), CoTMPP and FeCoTMPP, and metal phthalocyanine (Pc), FePc, CoPc and FeCuPc, supported on Ketjenblack (KJB) carbon. Iron phthalocyanine supported on KJB (FePc-KJB) carbon demonstrated higher activity towards oxygen reduction than Pt in neutral media. The effect of carbon substrate was investigated by evaluating FePc on Vulcan XC carbon (FePcVC) versus Ketjenblack carbon. FePc-KJB showed higher activity than FePcVC suggesting the catalyst activity could be improved by using carbon substrate with a higher surface area. With FePc-KJB as the MFC cathode catalyst, a power density of 634 mW m⁻² was achieved in 50 mM phosphate buffer medium at pH 7, which was higher than that obtained using the precious-metal Pt cathode (593 mW m⁻²). Under optimum operating conditions (i.e. using a high surface area carbon brush anode and 200 mM PBM as the supporting electrolyte with 1 g L⁻¹ acetate as the substrate), the power density was increased to 2011 mW m⁻². This high power output indicates that MFCs with low cost metal macrocycles catalysts is promising in further practical applications.     

Improved performance of air-cathode single-chamber microbial fuel cell for wastewater treatment using microfiltration membranes and multiple sludge inoculation

Substantial optimization and cost reduction are required before microbial fuel cells (MFCs) can be practically applied. We show here the performance improvement of an air-cathode single-chamber MFC by using a microfiltration membrane (MFM) on the water-facing side of the cathode and using multiple aerobic sludge (AES), anaerobic sludge (ANS), and wetland sediment (WLS) as anodic inoculums. Batch test results show that the MFC with an MFM resulted in an approximately two-fold increase in maximum power density compared to the MFC with a proton exchange membrane (PEM). The Coulombic efficiency increased from 4.17% to 5.16% in comparison with the membrane-less MFC, without a significant negative effect on power generation and internal resistance. Overall performance of the MFC was also improved by using multiple sludge inoculums in the anode. The MFC inoculated with ANS + WLS produced the greatest maximal power density of 373 mW m⁻² with a substantially low internal resistance of 38 Ω. Higher power density with a decreased internal resistance was also achieved in MFC inoculated with ANS + AES and ANS + AES + WLS in comparison with those inoculated with only one sludge. The MFCs inoculated with AES + ANS achieved the highest Coulombic efficiency. Over 92% COD was removed from confectionery wastewater in all tested MFCs, regardless of the membrane or inoculum used.     

A graphene modified anode to improve the performance of microbial fuel cells

Graphene with a Brunauer-Emmett-Teller (BET) specific surface area of 264 m² g⁻¹ has been used as anodic catalyst of microbial fuel cells (MFCs) based on Escherichia coli (ATCC 25922). The electrochemical activities of plain stainless steel mesh (SSM), polytetra?uoroethylene (PTFE) modified SSM (PMS) and graphene modified SSM (GMS) have been investigated by cyclic voltammetry (CV), discharge experiment and polarization curve measurement. The GMS shows better electrochemical performance than those of SSM and PMS. The MFC equipped with GMS anode delivers a maximum power density of 2668 mW m⁻², which is 18 times larger than that obtained from the MFC with the SSM anode and is 17 times larger than that obtained from the MFC with the PMS anode. Scanning electron microscopy (SEM) results indicate that the increase in power generation could be attributed to the high surface area of anode and an increase in the number of bacteria attached to anode.     

Manganese dioxide-coated carbon nanotubes as an improved cathodic catalyst for oxygen reduction in a microbial fuel cell

To develop an efficient and cost-effective cathodic electrocatalyst for microbial fuel cells (MFCs), carbon nanotubes (CNTs) coated with manganese dioxide using an in situ hydrothermal method (in situ MnO₂/CNTs) have been investigated for electrochemical oxygen reduction reaction (ORR). Examination by transmission electron microscopy shows that MnO₂ is sufficiently and uniformly dispersed over the surfaces of the CNTs. Using linear sweep voltammetry, we determine that the in situ MnO₂/CNTs are a better catalyst for the ORR than CNTs that are simply mechanically mixed with MnO₂ powder, suggesting that the surface coating of MnO₂ onto CNTs enhances their catalytic activity. Additionally, a maximum power density of 210 mW m⁻² produced from the MFC with in situ MnO₂/CNTs cathode is 2.3 times of that produced from the MFC using mechanically mixed MnO₂/CNTs (93 mW m⁻²), and comparable to that of the MFC with a conventional Pt/C cathode (229 mW m⁻²). Electrochemical impedance spectroscopy analysis indicates that the uniform surface dispersion of MnO₂ on the CNTs enhanced electron transfer of the ORR, resulting in higher MFC power output. The results of this study demonstrate that CNTs are an ideal catalyst support for MnO₂ and that in situ MnO₂/CNTs offer a good alternative to Pt/C for practical MFC applications.     

Biofilm formation and electricity generation of a microbial fuel cell started up under different external resistances

To investigate the effects of external resistance on the biofilm formation and electricity generation of microbial fuel cells (MFCs), active biomass, the content of extracellular polymeric substances (EPS) and the morphology and structure of the biofilms developed at 10, 50, 250 and 1000 Ω are characterized. It is demonstrated that the structure of biofilm plays a crucial role in the maximum power density and sustainable current generation of MFCs. The results show that the maximum power density of the MFCs increases from 0.93 ± 0.02 W m⁻² to 2.61 ± 0.18 W m⁻² when the external resistance decreases from 1000 to 50 Ω. However, on further decreasing the external resistance to 10 Ω, the maximum power density decreased to 1.25 ± 0.01 W m⁻² because of a less active biomass and higher EPS content in the biofilm. Additionally, the 10 Ω MFC shows a highest maximum sustainable current of 8.49 ± 0.19 A m⁻². This result can be attributed to the existence of void spaces beneficial for proton and buffer transport within the anode biofilm, which maintains a suitable microenvironment for electrochemically active microorganisms.