A membraneless microfluidic fuel cell with continuous multistream flow through cotton threads

In typical membraneless microfluidic fuel cells, the anolyte and catholyte are driven by syringe pumps, increasing the overall size of the system and limiting its miniaturization. In this study, a membraneless microfluidic fuel cell with continuous multistream flow through cotton threads was proposed. Cotton threads are simply laid in parallel to form flow channels. Multistream flow through cotton threads is formed without any external pumps. Cell performances under various operation conditions are evaluated. The results show that the middle stream could separate other two streams effectively to prevent the diffusive mixing of anolyte and catholyte. A peak power density of 19.9 mW cm⁻² and a limiting current density of 111.2 mA cm⁻² are delivered. Moreover, the performance improves with the sodium formate concentration rising up to 2M, while it declines at 4M fuel concentration due to the weakened convection transport and product removal caused by the low flow rate. With increasing the flow rate, the performance is enhanced because of the improved fuel transport at the anode. The good performance as well as the constant-voltage discharging curve indicates that the microfluidic fuel cell with cotton threads as flow channels provides a new direction for miniature power sources.     

In situ visualization of biofilm formation in a microchannel for a microfluidic microbial fuel cell anode

A novel in situ approach is proposed to visualize biofilm formation in the microchannel for the microfluidic microbial fuel cell (MMFC) anode, which could reflect a more precise biofilm formation during start-up process in real-time. A microchannel reactor was designed and fabricated based on a transparent indium-tin-oxide (ITO) conductive membrane. In situ visualization of biofilm formation under various anolyte flow rates was captured by a phase contrast microscope combined with a custom long working distance objective. The results show that no steady biofilm is formed on the surface of anode under low flow rate of 50 μL min^?1 because of the insufficient nutrient supply. With increasing the anolyte flow rate, more attached bacteria on the anode surface and denser biofilm are observed in the microchannel. Less bacteria are attached on the surface of anode along flow direction due to the entrance effect. However, denser biofilm leads to larger mass transfer resistance of the anolyte and product in biofilm. Therefore, a superior bioelectrochemical performance is yielded for the biofilm formed under a moderate flow rate during start-up process.     

Optimization of catholyte concentration and anolyte pHs in two chamber microbial electrolysis cells

The hydrogen production rate in a microbial electrolysis cell (MEC) using a non-buffered saline catholyte (NaCl) can be optimized through proper control of the initial anolyte pH and catholyte NaCl concentration. The highest hydrogen yield of 3.3 ± 0.4 mol H₂/mole acetate and gas production rate of 2.2 ± 0.2 m³ H₂/m³/d were achieved here with an initial anolyte pH = 9 and catholyte NaCl concentration of 98 mM. Further increases in the salt concentration substantially reduced the anolyte pH to as low as 4.6, resulting in reduced MEC performance due to pH inhibition of exoelectrogens. Cathodic hydrogen recovery was high (r_cat > 90%) as hydrogen consumption by hydrogenotrophic methanogens was prevented by separating the anode and cathode chambers using a membrane. These results show that the MEC can be optimized for hydrogen production through proper choices in the concentration of a non-buffered saline catholyte and initial anolyte pH in two chamber MECs.     

A direct formate microfluidic fuel cell with cotton thread-based electrodes

A direct formate microfluidic fuel cell with cotton thread-based electrodes is proposed. The palladium catalyst is directly coated on cotton threads by repeated dipping method to prepare electrodes, which integrates the flow channel and electrode together and provides exposed active sites for enhancing the mass transfer on the anode and cathode. The aqueous anolyte and catholyte transport through cotton threads by capillary force with aid of gravity, eliminating the use of any external pump and facilitating the integration and miniaturization of the whole system. In the experiment, a three-flow channel structure is employed. The fuel is sodium formate and the oxidant is hydrogen peroxide. 1 M Na₂SO₄ solution is introduced into the middle channel formed by cotton threads with no catalyst to alleviate the reactant crossover. Performance is evaluated under various catalyst loadings, fuel concentrations and differences in height between the inlet and outlet. Results show that the fuel cell produces an open circuit voltage (OCV) of 1.41 V. The maximum current density of 74.56 mA cm⁻² and the peak power density of 24.75 mW cm⁻² are yielded when the palladium loading is 1 mg cm⁻¹ and the difference in height between the inlet and outlet is 7 cm, using 4 M HCOONa as fuel. Furthermore, the performance of the fuel cell increases first and then decreases with increasing the palladium loading. The same variation is observed with increasing the fuel concentration. However, the performance gradually increases with increasing the difference in height from 3 cm to 7 cm. The proposed microfluidic fuel cell with cotton thread-based electrodes shows enormous potential as a micro power source for portable devices.     

Bipolar polymer electrolyte interfaces for hydrogen–oxygen and direct borohydride fuel cells

Direct borohydride fuel cells (DBFCs) using liquid hydrogen peroxide as the oxidant are safe and attractive low temperature power sources for unmanned underwater vehicles (UUVs) as they have excellent energy and power density and do not feature compressed gases or a flammable fuel stream. One challenge to this system is the disparate pH environment between the anolyte fuel and catholyte oxidant streams. Herein, a bipolar interface membrane electrode assembly (BIMEA) is demonstrated for maintaining pH control of the anolyte and catholyte compartments of the fuel cell. The prepared DBFC with the BIMEA yielded a promising peak power density of 110 mW cm⁻². This study also investigated the same BIMEA for a hydrogen–oxygen fuel cell (H₂–O₂ FC). The type of gas diffusion layer used and the gas feed relative humidity were found to impact fuel cell performance. Finally, a BIMEA featuring a silver electrocatalyst at the cathode in a H₂–O₂ FC was successfully demonstrated.     

Effect of anolyte pH and cathode Pt loading on electricity and hydrogen co-production performance of the bio-electrochemical system

In a novel bio-electrochemical system (BES) for hydrogen and electricity co-production with acetate substrate, the anolyte pH and cathode Pt loading effects are investigated to improve the cell performance for hydrogen and electricity co-production and reduce the cost. The optimized anolyte pH is 9. The maximum hydrogen production rate of 0.55 m³ m⁻³ d⁻¹ and COD removal of 76% are obtained under optimal anolyte pH in the present BES. Over high or over low anolyte pH decreases the hydrogen production rate and COD removal. In addition, the experiments show that there is no considerable difference for the power density output and steady state current when the Pt catalyst loading is above 0.1 mg cm⁻². But when the Pt catalyst loading is lower than 0.1 mg cm⁻², the power density output and current decreases significantly. About 1.7 W m⁻³ power density output can be obtained by using 0.1 mg cm⁻² Pt catalyst in the present research.     

Application of Pt loaded graphite felt in SO2-depolarized electrolyzer

The three-dimensional anodes for SO₂ depolarized electrolysis (SDE) cells are prepared by loading Pt/C on high void content graphite felts, with the method of ultrasonic spray and vacuum suction. SEM results confirm the three-dimensional space distribution of Pt in graphite felts, which ensures sufficient contact between Pt/C and SO₂ in anolyte. Comparing with the two-dimensional anodic catalyst layer loaded on the proton exchange membrane in a conventional SDE cell, the application of the three-dimensional anode decreases cell impedance greatly and improves the SDE performance significantly. In this study, 0.63 mg/cm² Pt loading amount shows the best performance when Pt/C is double-side-sprayed on graphite felt, and the current density reaches 1.24 A/cm² at cell voltage of 1.2 V, as operating at 60 °C and anolyte flow rate of 360 mL/min. The effects of the Pt loading amount, operating temperature and anolyte flow rate on the SDE performance are investigated.     

Effect of operating variables on performance of membrane electrolysis cell for carrying out Bunsen reaction of I–S cycle

Membrane electrolysis is coming up as one of the alternatives to direct contact mode of carrying out Bunsen reaction of I–S cycle. It has potential to reduce the use of excess iodine and water. A two-compartment membrane electrolysis cell with graphite electrodes and Nafion 117 membrane was used for Bunsen reaction. Effect of six independent variables on cell voltage was determined for current density values of up to 80 A/dm². The variables were anolyte pressure, catholyte pressure, temperature, sulphuric acid concentration, HI concentration, and I₂/HI molar ratio in catholyte. Flow rate of anolyte and catholyte were identified where mass transfer resistance was not significant before performing experiments with different independent variables. Cell voltage was analysed by identifying three different regimes based on its variation with current density and current density ranges where electrode resistance or ohmic resistance dominated are identified. Current efficiency was measured for 1 A/dm² and was found to be close to 100% irrespective of values of the independent variable. Minimum amount of heat equivalent of electric energy required for membrane electrolysis was calculated and increase in its value with increase in sulphuric acid concentration was compared with estimate of reduction in heat required for concentration of sulphuric acid.     

Effects of mediator producer and dissolved oxygen on electricity generation in a baffled stacking microbial fuel cell treating high strength molasses wastewater

The effects of Pseudomonas aeruginosa, pyocyanin, and influent dissolved oxygen (DO) on the electricity generation in a baffled stacking microbial fuel cell (MFC) treating high strength molasses wastewater were investigated. The result shows that the influent chemical oxygen demand (COD) of 500–1000 mg l⁻¹ had the optimal substrate-energy conversion rate. The addition of a low density of P. aeruginosa (8.2 mg l⁻¹) or P. aeruginosa with pyocyanin improved the COD removal and power generation. This improvement could be attributed to the enhancement of electron transfer with the help of redox mediators. Influent DO at a concentration of up to 1.22 mg l⁻¹ did not inhibit the electricity generation. Large proportions of COD, organic-N and total-N were removed by the MFC. The MFC effluent was highly biodegradable. Denaturing gradient gel electrophoresis analysis shows that the added pyocyanin resided in the MFC for up to 14 days. An analysis of anode voltage reveals that microbial proton transport to the cathode was importantly responsible for the internal resistance.     

Effect of inert particle concentration on the operation of a microbial fuel cell

Considering the promising application of microbial fuel cells (MFCs) in the wastewater treatment, the inherent solid particles in the wastewater may affect the MFC performance. In this paper, the effect of inert particle concentration on the operation of MFCs is investigated by adding silicon dioxide (SiO₂) particles into the anolyte. The results show that the existing SiO₂ particles in the anolyte result in a decreased active biomass and a reduced electrochemical activity of the biofilm. The anode ohmic resistance is almost the same for MFCs with various SiO₂ particle concentrations in the anolyte, while an increase in the charge transfer resistance is observed. A small amount of inert particles have little influence on the MFC. However, when the MFC is operated with the anolyte containing more than 500 mg L⁻¹ SiO₂ particles, the performance decreases significantly due to the low electrochemical activity and high internal resistance of the anode.     

Investigation of bubble effect in microfluidic fuel cells by a simplified microfluidic reactor

This study experimentally examines the influence of two-phase flow on the fluid flow in membraneless microfluidic fuel cells. The gas production rate from such fuel cell is firstly estimated via corresponding electrochemical equations and stoichiometry from the published measured current–voltage curves in the literature to identify the existence of gas bubble. It is observed that O₂ bubble is likely to be generated in Hasegawa’s experiment when the current density exceeds 30 mA cm^?2 and 3 mA cm^?2 for volumetric flow rates of 100 μL min^?1 and 10 μL min^?1, respectively. Besides, CO₂ bubble is also likely to be presented in the Jayashree’s experiment at a current density above 110 mA cm^?2 at their operating volumetric liquid flow rate, 0.3 mL min^?1. Secondly, a 1000-μm-width and 50-μm-depth platinum-deposited microfluidic reactor is fabricated and tested to estimate the gas bubble effect on the mixing in the similar microchannel at different volumetric flow rates. Analysis of the mixing along with the flow visualization confirm that the membraneless fuel cell should be free from any bubble, since the mixing index of the two inlet streams with bubble generation is almost five times higher than that without any bubble at the downstream.     

Enhanced hydrogen generation using a saline catholyte in a two chamber microbial electrolysis cell

High rates of hydrogen gas production were achieved in a two chamber microbial electrolysis cell (MEC) without a catholyte phosphate buffer by using a saline catholyte solution and a cathode constructed around a stainless steel mesh current collector. Using the non-buffered salt solution (68 mM NaCl) produced the highest current density of 131 ± 12 A/m³, hydrogen yield of 3.2 ± 0.3 mol H₂/mol acetate, and gas production rate of 1.6 ± 0.2 m³ H₂/m³·d, compared to MECs with catholytes externally sparged with CO₂ or containing a phosphate buffer. The salinity of the catholyte achieved a high solution conductivity, and therefore the electrode spacing did not appreciably affect performance. The coulombic efficiency with the cathode placed near the membrane separating the chambers was 83 ± 4%, similar to that obtained with the cathode placed more distant from the membrane (84 ± 4%). Using a carbon cloth cathode instead of the stainless steel mesh cathode did not significantly affect performance, with all reactor configurations producing similar performance in terms of total gas volume, COD removal, r_cat and overall energy recovery. These results show MEC performance can be improved by using a saline catholyte without pH control.     

The importance of OH− transport through anion exchange membrane in microbial electrolysis cells

In two-chamber microbial electrolysis cells (MECs) with anion exchange membranes (AEMs), a phosphate buffer solution (PBS) is typically used to avoid increases in catholyte pH as Nernst equation calculations indicate that high pHs adversely impact electrochemical performance. However, ion transport between the chambers will also impact performance, which is a factor not included in those calculations. To separate the impacts of pH and ion transport on MEC performance, a high molecular weight polymer buffer (PoB), which was retained in the catholyte due to its low AEM transport and cationic charge, was compared to PBS in MECs and abiotic electrochemical half cells (EHCs). In MECs, catholyte pH control was less important than ion transport. MEC tests using the PoB catholyte, which had a higher buffer capacity and thus maintained a lower catholye pH (<8), resulted in a 50% lower hydrogen production rate (HPR) than that obtained using PBS (HPR = 0.7 m³-H₂ m^?3 d^?1) where the catholyte rapidly increased to pH = 12. The main reason for the decreased performance using PoB was a lack of hydroxide ion transfer into the anolyte to balance pH. The anolyte pH in MECs rapidly decreased to 5.8 due to a lack of hydroxide ion transport, which inhibited current generation by the anode, whereas the pH was maintained at 6.8 using PBS. In abiotic tests in ECHs, where the cathode potential was set at ?1.2 V, the HPR was 133% higher using PoB than PBS due to catholyte pH control, as the anolyte pH was not a factor in the performance. These results show that maintaining charge transfer to control anolyte pH is more important than obtaining a more neutral pH catholyte.     

Bubble behavior and photo-hydrogen production performance of photosynthetic bacteria in microchannel photobioreactor

A transparent microchannel photobioreactor was manufactured to visualize the colony formation of photosynthetic bacteria (PSB), Rhodopseudomonas palustris CQK 01, as well as the biogas bubble behavior within the microstructure. The results showed that the formation of PSB colony in the interior of microchannels can be divided into four stages: bacteria absorption, bacteria reproduction, morphological transformation and colony formation. It was founded that the microchannel vents immobilized by PSB colony was the favorable sites for the emergence of biogas bubbles. In this work, the effects of substrate concentration and flow rate of the influent solution as well as illumination wavelength and intensity on the photo-hydrogen production performance of the bioreactor were also investigated. The microchannel photobioreactor exhibited a maximal hydrogen production rate of 1.48 mmol/g cell dry weight/h, maximal hydrogen yield of 0.91 mol H₂/mol glucose in all tests at an optimal inlet medium flow rate of 2.8 ml/h and substrate concentration of 50 mmol/l. In addition, photobioreactor showed a highest performance of hydrogen production and substrate consumption at 590 nm illumination wavelength and 5000 lx illumination intensity.     

A development of direct hydrazine/hydrogen peroxide fuel cell

A direct hydrazine fuel cell using H₂O₂ as the oxidizer has been developed. The N₂H₄/H₂O₂ fuel cell is assembled by using Ni-Pt/C composite catalyst as the anode catalyst, Au/C as the cathode catalyst, and Nafion membrane as the electrolyte. Both anolyte and catholyte show significant influences on cell voltage and cell performance. The open-circuit voltage of the N₂H₄/H₂O₂ fuel cell reaches up to 1.75 V when using alkaline N₂H₄ solution as the anolyte and acidic H₂O₂ solution as the catholyte. A maximum power density of 1.02 W cm⁻² has been achieved at operation temperature of 80 °C. The number of electrons exchanged in the H₂O₂ reduction reaction on Au/C catalyst is 2.     

Magnesium-solution phase catholyte semi-fuel cell for undersea vehicles

A magnesium-solution phase catholyte semi-fuel cell (SFC) is under development at the Naval Undersea Warfare Center (NUWC) as an energetic electrochemical system for low rate, long endurance undersea vehicle applications. This electrochemical system consists of a magnesium anode, a sodium chloride anolyte, a conductive membrane, a catalyzed carbon current collector, and a catholyte of sodium chloride, sulfuric acid and hydrogen peroxide.Bipolar electrode fabrication to minimize cell stack volume, long duration testing, and scale-up of electrodes from 77 to 1000 cm² have been the objectives of this project. Single cell and multi-cell testing at the 77 cm² configuration have been utilized to optimize all testing parameters including start-up conditions, flow rates, temperatures, and electrolyte concentrations while maintaining high voltages and efficiencies. The fabrication and testing of bipolar electrodes and operating parameter optimization for large electrode area cells will be presented. Designs for 1000 cm² electrodes, electrolyte flow patterns and current/voltage distribution across these large area cells will also be discussed.     

Numerical study of the effect of the channel and electrode geometry on the performance of microfluidic fuel cells

Using COMSOL Multiphysics 3.5, 3D numerical models of different microfluidic fuel cells have been developed in this paper to determine the effect of different modifications which have been implemented in the microfluidic fuel cell since its advent. These modifications include the channel geometry aspect ratio and electrode configuration, the third flow between the anolyte and catholyte in the channel (i.e., multi-stream laminar flow), and multiple periodically placed inlets. To be consistent with the convention, the output power of the device is normalized by the electrode surface area; however, the power density calculations are also performed through normalization by the device volume. It is shown that the latter method is more realistic and providing more information from the design point of view since the ultimate goal in designing the microfluidic fuel cell is to fabricate a compact, yet powerful device. Finally, a novel design of the microfluidic fuel cell with a tapered channel is suggested and compared to the non-tapered geometry through the polarization curves. The steps which have been taken in COMSOL to obtain these polarization curves are clearly and thoroughly explained. The Butler-Volmer equation was implemented to incorporate for the electrochemical reactions at the electrodes. The “Conductive Media DC” module, in COMSOL, is used to model the electric fields within the fuel cell. The concentration distributions of the reactant species are obtained using the “Incompressible Navier-Stokes” and “Convection and Diffusion” modules. Solving these equations together predicts the current density for given cell voltage values. The results demonstrate the cell voltage losses due to activation, ohmic and concentration overpotentials. It is shown that for a fixed value of the cell voltage (say 0.45 V), the fuel cell with multiple periodically placed inlets has the highest fuel utilization (i.e., 62.3%); while the “Simple square” geometry depicts 13.8% fuel utilization at this potential. Thus, the multiple-inlets design is particularly suitable for low-voltage applications which require high current. Also, the results of the tapered geometry proposed in this paper show that tapering the channel enhances the polarization curve comparing to the square cross-section geometry with extended electrodes. In essence, the fuel utilization of the “Extended square” geometry is increased from 15.4% to 57.6% by tapering the channel. This is due to the fact that the mixing region growth rate is restricted in the tapered geometry, and hence the electrodes on the top and bottom walls of the channel can be more extended toward the centre of the channel before the crossover occurs.     

Electrochemical performance of a glucose/oxygen microfluidic biofuel cell

A microfluidic glucose/O₂ biofuel cell, delivering electrical power, is developed based on both laminar flow and biological enzyme strategies. The device consists of a Y-shaped microfluidic channel in which fuel and oxidant streams flow laminarly in parallel at gold electrode surfaces without convective mixing. At the anode, the glucose is oxidized by the enzyme glucose oxidase whereas at the cathode, the oxygen is reduced by the enzyme laccase, in the presence of specific redox mediators. Such cell design protects the anode from interfering parasite reaction of O₂ at the anode and works with different streams of oxidant and fuel for optimal operation of the enzymes. The dependence of the flow rate on the current is evaluated in order to determine the optimum flow that would provide little to no mixing while yielding high current densities. The maximum power density delivered by the assembled biofuel cell reaches 110 μW cm⁻² at 0.3 V with 10 mM glucose at 23 °C. This research demonstrates the feasibility of advanced microfabrication techniques to build an efficient microfluidic glucose/O₂ biofuel cell device.     

Effect of dissolved oxygen concentration on nitrogen removal and electricity generation in self pH-buffer microbial fuel cell

A double-chamber self pH-buffer microbial fuel cell (MFC) was used to investigate the effect of dissolved oxygen (DO) concentration on cathodic nitrification coupled with anodic denitrification MFC. It was found that nitrogen and COD removal, electricity generation were positively correlated with DO concentration in the cathode chamber. When total inorganic nitrogen of influent was 202.51 ± 7.82 mg/L at DO 6.8 mg/L, the maximum voltage output was 282 mV and the maximum power density was 149.76 mW/m². After 82 h operation, the highest removal rate of total inorganic nitrogen was 91.71 ± 0.38%. Electrochemical impedance spectroscopy (EIS) test showed that the internal resistance of the reactor with different DO concentration was related to the diffusion internal resistance. The data of bacterial analysis in the cathode chamber revealed that there were not only ammonia-oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB), but also a large number of exoelectrogens. Compared with the traditional biological denitrification and related MFC denitrification research, this method does not need pH-buffer solution and external circulation device through the anion exchange membrane (AEM). It can generate electricity and remove nitrogen simultaneously, and the oxygen utilization rate in the cathode can also be enhanced.     

Analysis of membraneless fuel cell using laminar flow in a Y-shaped microchannel

In this study, we implemented a theoretical analysis for a novel microfluidic fuel cell that utilizes the occurrence of laminar flows in a Y-shaped microchannel to keep the separation of fuel and oxidant streams without turbulent mixing. The liquid fuel and oxidant streams enter the system at different inlets, and then merge and flow in parallel to one another through the channel between two electrodes without the need of a membrane to separate both streams. A theoretical model containing the flow kinetics, species transport, and electrochemical reactions within the channel and the electrodes is developed with appropriate boundary conditions and solved by a commercial CFD package. The performance of this novel fuel cell is analyzed by a systematic study with respect to some important physical factors and the geometric effect of channel size. Results indicate that the performance is primarily dominated by the mass transport to the electrodes especially at the cathode and could be raised significantly by using a high aspect ratio of cross-sectional geometry.