Performance of a microfluidic microbial fuel cell based on graphite electrodes

A microfluidic microbial fuel cell utilizing the laminar flow to separate the anolyte and catholyte streams based on graphite electrode is proposed. The co-laminar flow of the two streams inside the microchannel is visualized under different flow rates. The effects of the acetate concentration and flow rate on the cell performance are investigated. The results show that the cell performance initially increases and then decreases with increasing influent COD concentration and the anolyte flow rate. The microfluidic microbial fuel cell produces a peak power density of 618 ± 4 mW/m² under the conditions of 1500 mg/L influent COD and an anolyte flow rate of 10 mL/h. The low internal resistance of fuel cell results from elimination of the proton exchange membrane and high surface-to-volume ratio of the microfluidic structure. Moreover, the thickness of biofilm decreases gradually along the flow direction of the microchannel due to the diffusive mixing of the catholyte.     

A review on membraneless laminar flow-based fuel cells

The review article provides a methodical approach for understanding membraneless laminar flow-based fuel cells (LFFCs), also known as microfluidic fuel cells. Membraneless LFFCs benefit from the lamination of multiple streams in a microchannel. The lack of convective mixing leads to a well-defined liquid-liquid interface. Usually, anode and cathode are positioned at both sides of the interface. The liquid-liquid interface is considered as a virtual membrane and ions can travel across the channel to reach the other side and complete the ionic conduction. The advantage of membraneless LFFC is the lack of a physical membrane and the related issues of membrane conditioning can be eliminated or becomes less important. Based on the electrode architectures, membraneless LFFCs in the literature can be categorized into three main types: flow-over design with planar electrodes, flow-through design with three-dimensional porous electrodes, and membraneless LFFCs with air-breathing cathode. Since this paper focuses on reviewing the design considerations of membraneless LFFCs, a concept map is provided for understanding the cross-related problems. The impacts of flow and electrode architecture on cell performance and fuel utilization are discussed. In addition, the main challenges and key issues for further development of membraneless LFFCs are discussed.     

Sequential flow membraneless microfluidic fuel cell with porous electrodes

A novel convective flow membraneless microfluidic fuel cell with porous disk electrodes is described. In this fuel cell design, the fuel flows radially outward through a thin disk shaped anode and across a gap to a ring shaped cathode. An oxidant is introduced into the gap between anode and cathode and advects radially outward to the cathode. This fuel cell differs from previous membraneless designs in that the fuel and the oxidant flow in series, rather than in parallel, enabling independent control over the fuel and oxidant flow rate and the electrode areas. The cell uses formic acid as a fuel and potassium permanganate as the oxidant, both contained in a sulfuric acid electrolyte. The flow velocity field is examined using microscale particle image velocimetry and shown to be nearly axisymmetric and steady. The results show that increasing the electrolyte concentration reduces the cell Ohmic resistance, resulting in larger maximum currents and peak power densities. Increasing the flow rate delays the onset of mass transport and reduces Ohmic losses resulting in larger maximum currents and peak power densities. An average open circuit potential of 1.2 V is obtained with maximum current and power densities of 5.35 mA cm⁻² and 2.8 mW cm⁻², respectively (cell electrode area of 4.3 cm²). At a flow rate of 100 μL min⁻¹ a fuel utilization of 58% is obtained.     

Microfluidic fuel cells: A review

A microfluidic fuel cell is defined as a fuel cell with fluid delivery and removal, reaction sites and electrode structures all confined to a microfluidic channel. Microfluidic fuel cells typically operate in a co-laminar flow configuration without a physical barrier, such as a membrane, to separate the anode and the cathode. This review article summarizes the development of microfluidic fuel cell technology, from the invention in 2002 until present, with emphasis on theory, fabrication, unit cell development, performance achievements, design considerations, and scale-up options. The main challenges associated with the current status of the technology are provided along with suggested directions for further research and development. Moreover, microfluidic fuel cell architectures show great potential for integration with biofuel cell technology. This review therefore includes microfluidic biofuel cell developments to date and presents opportunities for future work in this multi-disciplinary field.     

Air-breathing membraneless laminar flow-based fuel cell with flow-through anode

This paper describes a detailed characterization of laminar flow-based fuel cell (LFFC) with air-breathing cathode for performance (fuel utilization and power density). The effect of flow-over and flow-through anode architectures, as well as operating conditions such as different fuel flow rates and concentrations on the performance of LFFCs was investigated. Formic acid with concentrations of 0.5 M and 1 M in a 0.5 M sulfuric acid solution as supporting electrolyte were exploited with varying flow rates of 20, 50, 100 and 200 μl/min. Because of the improved mass transport to catalytic active sites, the flow-through anode showed improved maximum power density and fuel utilization per single pass compared to flow-over planar anode. Running on 200 μl/min of 1 M formic acid, maximum power densities of 26.5 mW/cm² and 19.4 mW/cm² were obtained for the cells with flow-through and flow-over anodes, respectively. In addition, chronoamperometry experiment at flow rate of 100 μl/min with fuel concentrations of 0.5 M and 1 M revealed average current densities of 34.2 mA/cm² and 52.3 mA/cm² with average fuel utilization of 16.3% and 21.4% respectively for flow-through design. The flow-over design had the corresponding values of 25.1 mA/cm² and 35.5 mA/cm² with fuel utilization of 11.1% and 15.7% for the same fuel concentrations and flow rate.     

Counter flow membraneless microfluidic fuel cell

A counter flow membraneless microfluidic fuel cell is presented, where a non-reacting electrolyte separates the reacting streams. In this fuel cell design, vanadium reactants flow through porous carbon electrocatalysts. A sulfuric acid stream is introduced in the gap between the electrodes and diverts the reactants to opposite and independent outlets. This fuel cell differs from other membraneless designs in its ability to maintain a constant separation between the reactants without diffusive mixing.     

A membraneless microfluidic fuel cell stack

A membraneless microfluidic fuel cell stack architecture is presented that reuses reactants from one cell to a subsequent one, analogous to PEMFC stacks. On-chip reactant reuse improves fuel utilization and power densities relative to single cells. The reactants flow separately through porous electrodes and interface with a non-reacting and conductive electrolyte which maintains their separation. The reactants remain separated downstream of the interface and are used in subsequent downstream cells. This fuel cell uses porous carbon for electrocatalysts and vanadium redox species as reactants with a sulfuric acid supporting electrolyte. The overall power density of the fuel cell increases with reactant flow rate and decreasing the separating electrolyte flow rate. The peak power, maximum fuel utilization, and efficiency nearly double when electrically connecting the cells in parallel.     

Planar and three-dimensional microfluidic fuel cell architectures based on graphite rod electrodes

We propose new membraneless microfluidic fuel cell architectures employing graphite rod electrodes. Commonly employed as mechanical pencil refills, graphite rods are inexpensive and serve effectively as both electrode and current collector for combined all-vanadium fuel/oxidant systems. In contrast to film-deposited electrodes, the geometry and mechanical properties of graphite rods enable unique three-dimensional microfluidic fuel cell architectures. Planar microfluidic fuel cells employing graphite rod electrodes are presented here first. The planar geometry is typical of microfluidic fuel cells presented to date, and permits fuel cell performance comparisons and the evaluation of graphite rods as electrodes. The planar cells produce a peak power density of 35 mW cm⁻² at 0.8 V using 2 M vanadium solutions, and provide steady operation at flow rates spanning four orders of magnitude. Numerical simulations and empirical scaling laws are developed to provide insight into the measured performance and graphite rods as fuel cell electrodes.     

On the performance of membraneless laminar flow-based fuel cells

This paper reports on the characterization and optimization of laminar flow-based fuel cells (LFFCs) for both performance and fuel utilization. The impact of different operating conditions (volumetric flow rate, fuel-to-electrolyte flow rate ratio, and oxygen concentration) and of different cell dimensions (electrode-to-electrode distances, and channel length) on the performance (both power density and fuel utilization) of individual LFFCs is investigated. A finite-element-method simulation, which accounts for all relevant transport processes and electrode reactions, was developed to explain the experimental results here. This model can be used to guide further LFFC optimizations with respect to cell design and operation conditions. Using formic acid as the fuel, we measured a peak power density of 55 mW cm⁻². By hydrodynamically focusing the fuel to a thin stream on the anode we were able to reduce the fraction of fuel that passes through the channel without reacting, thereby increasing the fuel utilization per pass to a maximum of 38%. This paper concludes with a discussion on the various trade-offs between maximizing power density and optimizing fuel utilization per pass for individual LFFCs, in light of scaling out to a multichannel LFFC-based power source system.     

A woven thread-based microfluidic fuel cell with graphite rod electrodes

A woven thread-based microfluidic fuel cell based on graphite rod electrodes is proposed. Both inter-fiber gaps and inter-weave spaces could provide flow channels for the liquid transport through the woven cotton thread. Therefore, no external pumps are required to maintain the co-laminar flow, benefiting for the integration and miniaturization. In the experiment, sodium formate and hydrogen peroxide are used as fuel and oxidant, respectively. To improve the electrochemical reaction kinetics, KOH and H₂SO₄ serve as supporting electrolyte at the anode and cathode, respectively. Na₂SO₄ solution is used as the electrolyte to separate the cathode and anode in the middle flow channel and alleviate the reactant crossover. The open circuit potential of the fuel cell achieves 1.44 V and the maximum current density and power density are 56.6 mA cm^?2 and 20.7 mW cm^?2, respectively. Moreover, the cell performance reduces with increasing the electrode distance due to a high ohmic resistance. With an increase in the fuel concentration from 1 M to 4 M, the performance increases and it reduces with further increasing to 6 M owing to a correspondingly low flow rate. The highest fuel utilization rate reaches 10.9% at 4 M fuel concentration.     

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.     

Easy sintering of silver doped lanthanum strontium manganite current collector for solid oxide fuel cells

A new system, (La_0.8Sr_0.2)_1−xAg_xMnO_3+δ (LSAM, x ≤ 0.2), is developed as current collector for solid oxide fuel cell (SOFC). LSAM is prepared by a modified sol-gel method and presents a single phase. The shrinkage temperature reduces from 1150 °C to 800 °C with an addition of 15 mol% Ag to La_0.8Sr_0.2MnO_3+δ (LSM20). The contact resistance between the current collector and the cathode is measured, and the influence of Ag content on the contact resistance is investigated. The result shows that the contact resistance using (La_0.8Sr_0.2)_0.85Ag_0.15MnO_3+δ (LSAM15) as current collector is about 12 mΩ cm² at 750 °C, which is close to the value using expensive Pt paste as current collector. This new system is a promising current collecting material for the practical application of SOFC.     

Analyses of fuel utilization in microfluidic fuel cell

A microfluidic fuel cell is a miniature power source, which potentially could be used in micro electronic equipments, laptop computers, mobile phones and video cameras. In recent reports, the idea of a microfluidic fuel cell without using a polymer electrolyte membrane is proposed, whereby the laminar nature of the flow in the micro-channels is used to keep the anode and cathode streams separated such that adverse electrochemical reactions do not take place at the two electrode polarities. Since such cells are restricted by their size, improvement in fuel utilization would increase the cell efficiency by several degrees. In the present study, an improvement in fuel utilization is proposed by altering the design of the microfluidic fuel cell. In particular, a sulfuric acid stream is introduced between the fuel (HCOOH) and oxidizer (O₂ in H₂SO₄) streams to improve fuel utilization. Further improvement in fuel utilization is possible by changing the aspect ratio of the cell from 0.1 to 1. The fuel utilization of a cell with an aspect ratio of 0.1 is 14.1%, which increases to 16% when a sulfuric acid stream is introduced to prevent mixing of the fuel and oxidizer streams. The fuel utilization increases to 19% with the change in aspect ratio from 0.1 to 10, which further increases to 32% with the introduction of a sulfuric acid stream.     

Planar current collector design and fabrication for proton exchange membrane fuel cell

This paper proposes a novel planar type lightweight current collector for proton exchange membrane fuel cells (PEMFC) designed for low power portable applications. The proposed lightweight current collector, which is composed of a substrate, electrical conduction layer and corrosion resistance layer, combines the conventional metal sheet/mesh for current collecting and substrate together to reduce the possible distortion during operation caused by the mismatch due to large different mechanical properties between components. The current collector adopts FR-4 as the substrate material. The electrical conduction layer is made via coating a copper thin film using a thermo-evaporation layer. The corrosion resistance layer is made via coating a graphene thin film using spin coating and a vacuum oven process. Fabricated current collector sheet resistance measurements are conducted. The complete current collectors are assembled into a single cell PEMFC with both forced convection air-breathing cathode and self-air-breathing cathode. The related performance and stability experiments were conducted to investigate the feasibility for further applications.     

Characterization of bubble formation in microfluidic fuel cells employing hydrogen peroxide

In order to examine bubble evolution and discuss the effects of bubbles effect on the performance of microfluidic fuel cells, two 1.2-mm-depth microfluidic fuel cells employing 0.1-M H₂O₂ dissolved in 0.1-M NaOH solution and 0.05-M H₂SO₄ solution as fuel and oxidant, respectively, with transparent lids having width of 1.0 mm and 0.5 mm, are fabricated in the present study for both cell performance measurement and flow visualization. The results show that the present cells operating at either a higher volumetric flow or a smaller microchannel width yield both better performance and more violent bubble growth. The bubble growth rate, Q_g, in a given microfluidic fuel cell is almost the same at different regions of that cell at a given volumetric flow rate, i.e. 10⁻⁵ cm³ s⁻¹ and 5 × 10⁻⁵ cm³ s⁻¹, respectively, for cells having widths of 0.5 mm and 1.0 mm at Q_l = 0.05 mL min⁻¹, and slightly increases at higher volumetric flow rates. Furthermore, the present study reports approximately constant values of Q_g/C_dA at various volumetric flow rates, which are 2 × 10⁻² and 5 × 10⁻² cm³ s⁻¹ A⁻¹, respectively, for cells having channel widths of 0.5 mm and 1.0 mm. In addition, the 0.5-mm-wide cell has higher cell output and performs more tortuous polarization curve.     

Filter paper membrane based microfluidic fuel cells: Toward next-generation miniaturized and low cost power supply

Micro Fuel cells or microfluidic fuel cells (μMFCs) are one of the most promising power supplies for portable electronics. However, the necessary electrode spacing is required to prevent fuel-crossover and maintain the stable operation, introducing the unavoidable ohmic resistance and retarding the miniaturization. Herein, we propose a novel μMFC device combining the cellulose paper as separator, with selective catalysts at the cathode side to eliminate the unwanted side reactions and increase the system compactness. One single reactant solution containing fuel and electrolyte is applied to keep the device stable operation. The power-generation properties are evaluated in typical alkaline conditions. A great construction simplification makes the device a substantial high-power density of 2.14 W cm^?3 and maximum current density of 15.82 A cm^?3. The μMFC stacks are arranged in series and parallel manners, which delivers a maximum power output of 23.6 mW and current of 194.6 mA. It is expected that innovative and customizable performance from commercial paper and low-cost carbonaceous catalysts can provide a forum for future advancement in chip-based electrochemical energy generation and storage devices.     

Energy and exergy analysis of microfluidic fuel cell

Microfluidic fuel cell (MFC) is a promising fuel cell type because its membraneless feature implies great potential for low-cost commercialization. In this study, an energy and exergy analysis of MFC is performed by numerical simulation coupling computational fluid dynamics (CFD) with electrochemical kinetics. MFC system designs with and without fuel recirculation are investigated. The effects of micropump efficiency, fuel flow rate and fuel concentration on the MFC system performance are evaluated. The results indicate that fuel recirculation is preferred for MFC to gain higher exergy efficiency only if the efficiency of the micropump is sufficiently high. Optimal cell operating voltage for achieving the highest exergy efficiency can be obtained. Parasitic effect will cause a significant reduction in the exergy efficiency. An increase in the fuel concentration will also lead to a reduction in the exergy efficiency. Increasing the fuel flow rate in a MFC with fuel recirculation will cause a fluctuating variation in the exergy efficiency. On the other hand, in a one-off MFC system, the exergy efficiency decreases with increasing fuel flow rate. The present work enables better understanding of the energy conversion in MFC and facilitates design optimization of MFC.     

Surface modified Ni foam as current collector for syngas solid oxide fuel cells with perovskite anode catalyst

Cu surface modified nickel foam is obtained by heating copper coated nickel foam in a reducing atmosphere. La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCM) perovskite oxide is prepared using a sol–gel combustion method. The modified foams and LSCM powders exhibit excellent resistance to carbon deposition in syngas at high temperatures. Furthermore, Cu modified foams show better mechanical strength compared to bare Ni foam, which readily cracks after exposure to syngas at high temperature. LSCM retains its perovskite structure during exposure to syngas or carbon monoxide at 900 °C for 10 h. Cu surface modified Ni foam current collector demonstrates good chemical compatibility with LSCM in syngas atmosphere at high temperature. Syngas solid oxide fuel cells (SOFCs) are assembled using Cu modified Ni foam anode current collector, LSCM anode catalyst, YSZ electrolyte, and porous Pt cathode. The present fuel cell provides similar power density to one with gold anode current collector and has excellent stability during operation at 900 °C.     

Study on the levelling process of the current collector for the molten carbonate fuel cell based on curvature integration method

The current collector for the molten carbonate fuel cell (MCFC) is manufactured from the sheet metal forming process. After the forming process, the current collector is bent resulting in a specific curvature (κ_i) in the direction in which trapezoidal protrusions are formed due to springback. In the stack of the MCFC, small deformation of the current collector can bring about defects in the electrolyte, non-uniform contact and difficulties in assembling the stack. Therefore, the curvature of the current collector should be minimized in order to reduce defects which can cause critical damage in the long-term operation. In order to straighten the current collector, the levelling process using three rolls was employed. In this work, a simple and effective method for designing the levelling process was proposed. An analytic model and the finite element analysis were used in combination. The optimal curvature minimizing the resultant curvature and the resultant moment of the current collector down to zero was calculated from the bending moment–curvature relationship. The bending moment–curvature relationship of the current collector was determined from the finite element analysis of uniform bending using the simulation results of the three-stage forming process. In the analytic model based on curvature integration method, the proper roll arrangement corresponding to the optimal curvature was calculated. Experiments were conducted using the calculated roll arrangement. The current collector was levelled nearly flat using the levelling process. After the levelling process, the flattened current collector was easily assembled with a centre plate and ensuring uniform contact with the electrolyte.     

Mass transfer and performance of membrane-less micro fuel cell: A review

Membrane-less micro fuel cells (MMFCs) are high potential alternative power sources compared to conventional batteries. They use the advantage of laminar flow without the presence of a membrane to separate the anode and the cathode. This article is a wide-ranging review of recent studies on mass transfer, performance, modelling advances and future opportunity in MMFCs research. The discussion focuses on the critical factors that limit the performance of MMFCs. Because MMFCs are diffusion-limited, most of this review focuses on design considerations to enhance the power density output. Moreover, the current status of computational modelling for MMFC systems to upgrade the cell performance will be presented. The review also identifies the challenges and opportunities available for increasing cell performance and making the MMFC a practical application device in the future.