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.     

Enlargement of anode for enhanced simultaneous azo dye decolorization and power output in air-cathode microbial fuel cell

Air-cathode, microbial fuel cells (MFC) with different anode surface areas were evaluated for simultaneous decolorization of Congo Red and bioelectricity production. Doubling the anode area from 18 to 36?cm² increased net power by 150?% (0.16–0.4?mW), normalized power (per anode surface area) by 22?% (88–107?mW?m^?2) and Congo Red decolorization by 163?% (1.6–4.2?mg?l^?1?h^?1). Quadrupling the original anode area induced an additional 5?% increase (up to 4.2?mW) in net power and 174?% increase (up to 11.5?mg?l^?1?h^?1) in Congo Red decolorization; however, normalized power decreased by 85?% (down to 58?mW?m^?2). Increased bacterial attachment could account for both the enhanced power and Congo Red decolorization in larger anode MFCs. The limited effect on power output likely arises from cathode limitation or inefficient utilization of anodes.     

Treatment of biodiesel production wastes with simultaneous electricity generation using a single-chamber microbial fuel cell

Biodiesel production through transesterification of lipids generates large quantity of biodiesel waste (BW) containing mainly glycerin. BW can be treated in various ways including distillation to produce glycerin, use as substrate for fermentative propanediol production and discharge as wastes. This study examined microbial fuel cells (MFCs) to treat BW with simultaneous electricity generation. The maximum power density using BW was 487 ± 28 mW/m² cathode (1.5 A/m² cathode) with 50 mM phosphate buffer solution (PBS) as the electrolyte, which was comparable with 533 ± 14 mW/m² cathode obtained from MFCs fed with glycerin medium (COD 1400 mg/L). The power density increased from 778 ± 67 mW/m² cathode using carbon cloth to 1310 ± 15 mW/m² cathode using carbon brush as anode in 200 mM PBS electrolyte. The power density was further increased to 2110 ± 68 mW/m² cathode using the heat-treated carbon brush anode. Coulombic efficiencies (CEs) increased from 8.8 ± 0.6% with carbon cloth anode to 10.4 ± 0.9% and 18.7 ± 0.9% with carbon brush anode and heat-treated carbon brush anode, respectively.     

Sustained generation of electricity by the spore-forming,Gram-positive, <Emphasis Type="Italic">Desulfitobacterium hafniense</Emphasis> strain DCB2

Desulfitobacterium hafniense strain DCB2 generates electricity in microbial fuel cells (MFCs) when humic acids or the humate analog anthraquinone-2,6-disulfonate (AQDS) is added as an electron-carrying mediator. When utilizing formate as fuel, the Gram-positive, spore-forming bacterium generated up to 400 mW/m² of cathode surface area in a single-chamber MFC with a platinum-containing air-fed cathode. Hydrogen, lactate, pyruvate, and ethanol supported electricity generation, but acetate, propionate, and butyrate did not. Scanning electron microscopy indicated that strain DCB2 colonized the surface of a current-generating anode but not of an unconnected electrode. The electricity was recovered fully within minutes after the exchange of the medium in the anode chamber and within a week after an exposure of a colonized anode to 90°C for 20 min. Of the six strains of Desulfitobacteria tested, all of which would reduce AQDS, only D. hafniense strain DCB2 continued to reduce AQDS and generate electricity for more than 24 h, indicating that reduction of the humate analog alone is insufficient to sustain electrode reduction.     

Electrochemical analysis of Clostridium propionicum and its acrylic acid production in microbial fuel cells

Currently, acrylic acid is produced at a low yield by the resting cells of Clostridium propionicum with the supplement of extra electron acceptors. As an alternative way, acrylic acid production coupled with electricity generation was achieved by C. propionicum‐based microbial fuel cells (MFCs). Electricity was generated in the salt‐bridge MFCs with cysteine and resazurin in the anode chamber as mediators, and K₃Fe(CN)₆ as the cathode electron acceptor. Power generation was 21.78 mW/m² with an internal resistance of 9809 Ω. Cyclic voltammograms indicated the main mechanism of power production was the electron transfer facilitated by mediators in the system. In the salt‐bridge MFC system, 0.694 mM acrylic acid was produced together with electricity generation.     

Application of Co-naphthalocyanine (CoNPc) as alternative cathode catalyst and support structure for microbial fuel cells

Co-naphthalocyanine (CoNPc) was prepared by heat treatment for cathode catalysts to be used in microbial fuel cells (MFCs). Four different catalysts (Carbon black, NPc/C, CoNPc/C, Pt/C) were compared and characterized using XPS, EDAX and TEM. The electrochemical characteristics of oxygen reduction reaction (ORR) were compared by cyclic voltammetry (CV) and linear sweep voltammetry (LSV). The Co-macrocyclic complex improves the catalyst dispersion and oxygen reduction reaction of CoNPc/C. The maximum power of CoNPc/C was 64.7 mW/m² at 0.25 mA as compared with 81.3 mW/m² of Pt/C, 29.7 mW/m² of NPc/C and 9.3 mW/m² of carbon black when the cathodes were implemented in H-type MFCs. The steady state cell, cathode and anode potential of MFC with using CoNPc/C were comparable to those of Pt/C.     

Solid phase microbial fuel cell (SMFC) for harnessing bioelectricity from composite food waste fermentation: influence of electrode assembly and buffering capacity

Solid phase microbial fuel cells (SMFC; graphite electrodes; open-air cathode) were designed to evaluate the potential of bioelectricity production by stabilizing composite canteen based food waste. The performance was evaluated with three variable electrode-membrane assemblies. Experimental data depicted feasibility of bioelectricity generation from solid state fermentation of food waste. Distance between the electrodes and presence of proton exchange membrane (PEM) showed significant influence on the power yields. SMFC-B (anode placed 5 cm from cathode-PEM) depicted good power output (463 mV; 170.81 mW/m²) followed by SMFC-C (anode placed 5 cm from cathode; without PEM; 398 mV; 53.41 mW/m²). SMFC-A (PEM sandwiched between electrodes) recorded lowest performance (258 mV; 41.8 mW/m²). Sodium carbonate amendment documented marked improvement in power yields due to improvement in the system buffering capacity. SMFCs operation also documented good substrate degradation (COD, 76%) along with bio-ethanol production. The operation of SMFC mimicked solid-sate fermentation which might lead to sustainable solid waste management practices.     

Improved performance of membrane free single-chamber air-cathode microbial fuel cells with nitric acid and ethylenediamine surface modified activated carbon fiber felt anodes

Surface modifications of anode materials are important for enhancing power generation of microbial fuel cell (MFC). Membrane free single-chamber air-cathode MFCs, MFC-A and MFC-N, were constructed using activated carbon fiber felt (ACF) anodes treated by nitric acid and ethylenediamine (EDA), respectively. Experimental results showed that the start-up time to achieve the maximum voltages for the MFC-A and MFC-N was shortened by 45% and 51%, respectively as compared to that for MFC-AT equipped with an unmodified anode. Moreover, the power output of MFCs with modified anodes was significantly improved. In comparison with MFC-AT which had a maximum power density of 1304 mW/m², the MFC-N achieved a maximum power density of 1641 mW/m². The nitric acid-treated anode in MFC-A increased the power density by 58% reaching 2066 mW/m². XPS analysis of the treated and untreated anode materials indicated that the power enhancement was attributable to the changes of surface functional groups.     

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.     

Investigating microbial fuel cell bioanode performance under different cathode conditions

A compact, three‐in‐one, flow‐through, porous, electrode design with minimal electrode spacing and minimal dead volume was implemented to develop a microbial fuel cell (MFC) with improved anode performance. A biofilm‐dominated anode consortium enriched under a multimode, continuous‐flow regime was used. The increase in the power density of the MFC was investigated by changing the cathode (type, as well as catholyte strength) to determine whether anode was limiting. The power density obtained with an air‐breathing cathode was 56 W/m³ of net anode volume (590 mW/m²) and 203 W/m³ (2160 mW/m²) with a 50‐mM ferricyanide‐based cathode. Increasing the ferricyanide concentration and ionic strength further increased the power density, reaching 304 W/m³ (3220 mW/m², with 200 mM ferricyanide and 200 mM buffer concentration). The increasing trend in the power density indicated that the anode was not limiting and that higher power densities could be obtained using cathodes capable of higher rates of oxidation. The internal solution resistance for the MFC was 5–6 Ω, which supported the improved performance of the anode design. A new parameter defined as the ratio of projected surface area to total anode volume is suggested as a design parameter to relate volumetric and area‐based power densities and to enable comparison of various MFC configurations. Published 2009 American Institute of Chemical Engineers Biotechnol. Prog., 2009     

Effect of vitamins and cell constructions on the activity of microbial fuel cell battery

Construction of efficient performance of microbial fuel cells (MFCs) requires certain practical considerations. In the single chamber microbial fuel cell, there is no border between the anode and the cathode, thus the diffusion of the dissolved oxygen has a contrary effect on the anodic respiration and this leads to the inhibition of the direct electron transfer from the biofilm to the anodic surface. Here, a fed-batch single chambered microbial fuel cells are constructed with different distances 3 and 6?cm (anode- cathode spacing), while keeping the working volume is constant. The performance of each MFC is individually evaluated under the effects of vitamins & minerals with acetate as a fed load. The maximum open circuit potential during testing the 3 and 6?cm microbial fuel cells is about 946 and 791?mV respectively. By decreasing the distance between the anode and the cathode from 6 to 3?cm, the power density is decreased from 108.3?mW?m^?2 to 24.5?mW?m^?2. Thus, the short distance in membrane-less MFC weakened the cathode and inhibited the anodic respiration which affects the overall performance of the MFC efficiency. The system is displayed a maximum potential of 564 and 791?mV in absence & presence of vitamins respectively. Eventually, the overall functions of the acetate single chamber microbial fuel cell can be improved by the addition of vitamins & minerals and increasing the distance between the cathode and the anode.     

A Universal Principle to Design Reversible Aqueous Batteries Based on Deposition–Dissolution Mechanism

Conventional charge storage mechanisms for electrode materials are common in widely exploited insertion/extraction processes, while some sporadic examples of chemical conversion mechanisms exist. It is perceived to be of huge potential, but it is quite challenging to develop new battery chemistry to promote battery performance. Here, an initiating and holistic deposition–dissolution battery mechanism for both cathodes and anodes is reported. A MnO₂–Cu battery based on this mechanism demonstrates outstanding energy density (27.7 mWh cm^?2), power density (1232 mW cm^?2), high reversibility, and unusual Coulombic efficiency. It can be charged to 0.8 mAh cm^?2 within 42 s and possessees a stable rate cyclability within vastly varied discharging current density (4–64 mA cm^?2). Moreover, the deposition–dissolution mechanism can be universally adopted and derived such that the corresponding MnO₂–Zn and MnO₂–Bi batteries are successfully constructed. The material selection principle, deposition–dissolution behaviors of cathode/anode materials, and battery performance are systematically elaborated. Since the electrodeposition chemistry is capable of involving a large family of materials, for example, metal oxides as cathode materials, or metals as anode materials, the research could be a model system to open a door to explore new aqueous battery materials and chemistry.     

Comparison of Electrode Reduction Activities of Geobacter sulfurreducens and an Enriched Consortium in an Air-Cathode Microbial Fuel Cell

An electricity-generating bacterium, Geobacter sulfurreducens PCA, was inoculated into a single-chamber, air-cathode microbial fuel cell (MFC) in order to determine the maximum electron transfer rate from bacteria to the anode. To create anodic reaction-limiting conditions, where electron transfer from bacteria to the anode is the rate-limiting step, anodes with electrogenic biofilms were reduced in size and tests were conducted using anodes of six different sizes. The smallest anode (7 cm², or 1.5 times larger than the cathode) achieved an anodic reaction-limiting condition as a result of a limited mass of bacteria on the electrode. Under these conditions, the limiting current density reached a maximum of 1,530 mA/m², and power density reached a maximum of 461 mW/m². Per-biomass efficiency of the electron transfer rate was constant at 32 fmol cell⁻¹ day⁻¹ (178 μmol g of protein⁻¹ min⁻¹), a rate comparable to that with solid iron as the electron acceptor but lower than rates achieved with fumarate or soluble iron. In comparison, an enriched electricity-generating consortium reached 374 μmol g of protein⁻¹ min⁻¹ under the same conditions, suggesting that the consortium had a much greater capacity for electrode reduction. These results demonstrate that per-biomass electrode reduction rates (calculated by current density and biomass density on the anode) can be used to help make better comparisons of electrogenic activity in MFCs.     

Performance of cathodic nitrate reduction driven by electricity generated from ANAMMOX sludge in anode

In this study, ANAMMOX sludge was used as anode microbial catalysts to drive electrocatalytic reduction of nitrate in the SnCu-Pd/CFC catalytic cathode with total nitrogen (TN) removal efficiency of ANAMMOX as well as generate electricity without additional carbon and energy source. The system operation with 1.74 Kg·N/m³·d as nitrogen loading rate (NLR) exhibited a TN removal efficiency of 96.3% and obtained the highest nitrogen removal rate (NRR, 1.69 Kg·N/m³·d), increased by 14.9% and 0.30 Kg·N/m³·d compared with open circuit (control group), respectively. Maximum voltage (39.8 mV) and power density (21.20 ± 0.05 mW/m³, standardized to anode surface area) were also observed. Additionally, microbial community analysis revealed community structure of S2_anode had an obvious disparity compared with others as the predominant ANAMMOX bacteria (AnAOB) closed to anode surface was evolved from Candidatus_Kuenenia to Candidatus_Brocadia.     

Metagenomic Analyses Reveal the Involvement of Syntrophic Consortia in Methanol/Electricity Conversion in Microbial Fuel Cells

Methanol is widely used in industrial processes, and as such, is discharged in large quantities in wastewater. Microbial fuel cells (MFCs) have the potential to recover electric energy from organic pollutants in wastewater; however, the use of MFCs to generate electricity from methanol has not been reported. In the present study, we developed single-chamber MFCs that generated electricity from methanol at the maximum power density of 220 mW m⁻² (based on the projected area of the anode). In order to reveal how microbes generate electricity from methanol, pyrosequencing of 16S rRNA-gene amplicons and Illumina shotgun sequencing of metagenome were conducted. The pyrosequencing detected in abundance Dysgonomonas, Sporomusa, and Desulfovibrio in the electrolyte and anode and cathode biofilms, while Geobacter was detected only in the anode biofilm. Based on known physiological properties of these bacteria, it is considered that Sporomusa converts methanol into acetate, which is then utilized by Geobacter to generate electricity. This speculation is supported by results of shotgun metagenomics of the anode-biofilm microbes, which reconstructed relevant catabolic pathways in these bacteria. These results suggest that methanol is anaerobically catabolized by syntrophic bacterial consortia with electrodes as electron acceptors.     

Effect of nitrogen addition on the performance of microbial fuel cell anodes

Carbon cloth anodes were modified with 4(N,N-dimethylamino)benzene diazonium tetrafluoroborate to increase nitrogen-containing functional groups at the anode surface in order to test whether the performance of microbial fuel cells (MFCs) could be improved by controllably modifying the anode surface chemistry. Anodes with the lowest extent of functionalization, based on a nitrogen/carbon ratio of 0.7 as measured by XPS, achieved the highest power density of 938 mW/m². This power density was 24% greater than an untreated anode, and similar to that obtained with an ammonia gas treatment previously shown to increase power. Increasing the nitrogen/carbon ratio to 3.8, however, decreased the power density to 707 mW/m². These results demonstrate that a small amount of nitrogen functionalization on the carbon cloth material is sufficient to enhance MFC performance, likely as a result of promoting bacterial adhesion to the surface without adversely affecting microbial viability or electron transfer to the surface.     

Fast‐Charging and Ultrahigh‐Capacity Lithium Metal Anode Enabled by Surface Alloying

Li metal anodes are going through a great revival but they still encounter grand challenges. One often neglected issue is that most reported Li metal anodes are only cyclable under relatively low current density (<5 mA cm^?2) and small areal capacity (<5 mAh cm^?2), which essentially limits their high‐power applications and results in ineffective Li utilization (<1%). Herein, it is reported that surface alloyed Li metal anodes can enable reversible cycling with ultrafast rate and ultralarge areal capacity. Low‐cost Si wafers are used and are chemically etched down to 20–30 µm membranes. Simply laminating a Si membrane onto Li foil results in the formation of Li_xSi alloy film fused onto Li metal with mechanical robustness and high Li‐ion conductivity. Symmetric cell measurements show that the surface alloyed Li anode has excellent cycling stability, even under high current density up to 25 mA cm^?2 and unprecedented areal capacity up to 100 mAh cm^?2. Furthermore, the surface alloyed Li anode is paired with amorphous MoS₃ cathode and achieves remarkable full‐cell performance.     

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.     

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.     

Filling the vacuum chamber of a technological system with homogeneous plasma using a stationary glow discharge

Experimental study of a glow discharge with electrostatic confinement of electrons is carried out in the vacuum chamber volume V ≈ 0.12 m³ of a technological system “Bulat-6” in argon pressure range 0.005–5 Pa. The chamber is used as a hollow cathode of the discharge with the inner surface area S ≈ 1.5 m². It is equipped with two feedthroughs, which make it possible to immerse in the discharge plasma interchangeable anodes with surface area S _a ranging from ∼0.001 to ∼0.1 m², as well as floating electrodes isolated from both the chamber and the anode. Dependences of the cathode fall U _c = 0.4−3 kV on the pressure p at a constant discharge current in the range I = 0.2−2 A proved that aperture of the electron escape out of the electrostatic trap is equal to the sum S _o = S _a + S _f of the anode surface S _a and the floating electrode surface S _f . The sum S _o defines the lower limit p _o of the pressure range, in which U _c is independent of p. At p < p _o the cathode fall U _c grows up dramatically, when the pressure decreases, and the pressure p tends to the limit p ^ex, which is in fact the discharge extinction pressure. At p ≈ p ^ex electrons emitted by the cathode and the first generation of fast electrons produced in the cathode sheath spend almost all their energy up to 3 keV on heating the anode and the floating electrode up to 600–800°C and higher. In this case the gas in the chamber is being ionized by the next generations of electrons produced in the cathode sheath, their energy being one order of magnitude lower. When S _a < (2m/M)^1/2 S, where m is the electron mass and M is the ion mass, the anode may be additionally heated by plasma electrons accelerated by the anode fall of potential U _a up to 0.5 kV.