A Data‐Driven Gaussian Process Regression Model for Two‐Chamber Microbial Fuel Cells

Rapidly and accurately modeling of microbial fuel cells (MFCs) plays an important role not only in thorough understanding of the effects of operating conditions on system performance, but also in the successful implementation of real‐time maximization of power output. Although the first principle electrochemical model has better generalization performance, it is often time‐consuming for model construction and is hard to real‐time application. In this study, a nonparametric Gaussian process regression (GPR) model is used to capture the nonlinear relationship between operating conditions and output voltage in the MFCs. A simple online learning strategy is proposed to recursively update the hyper‐parameters of the GPR model. The applicability and effectiveness of the proposed method is validated by both the simulation and experimental datasets from the acetate and the glucose and glutamic acid two‐chamber MFCs. The results illustrate that the online GPR model provides a promising method for capturing the complex nonlinearity phenomenon in MFCs, which can be greatly helpful for further real‐time optimization of MFCs.     

A Porous Silicon‐Based Ionomer‐Free Membrane Electrode Assembly for Miniature Fuel Cells

Previous work showed the pertinence of using grafted porous silicon as the proton exchange membrane for miniature fuel cells. One of the limitations was the membrane‐electrodes assembly, which required an ionomer, in the current study a 5% Nafion®‐117 solution, to ensure a proton‐conducting link between the commercial carbon cloth electrodes and the membrane. Here, new developments for this fuel cell, with a totally Nafion®‐free process, are reported. The Pt catalyst is sputtered and electrodeposited onto the surface of the proton conducting porous silicon membrane. The initial performance of this fuel cell is shown and demonstrates the validity of the technique.     

An Algorithm for On‐line Measurement of the Internal Resistance of Proton Exchange Membrane Fuel Cell

The internal resistance of proton exchange membrane fuel cell (PEMFC) system is difficult to measure on‐line due to its variation with time. The traditional electrochemical impedance spectroscopy (EIS) and its variants such as high frequency resistance (HFR) can be used to measure the resistance when the system is in steady state, but they fail in automotive applications where a change in speed or inclination modifications could lead to a sharp fluctuation in demand on power. In order to resolve this problem, a novel algorithm is proposed in this paper to estimate the resistance based on the alternating current (AC) impedance spectroscopy technique by adding an extra term to eliminate the errors caused by voltage variation or when the system is under unsteady state. Numerical simulations show that the proposed algorithm can not only accurately track the variation of the internal resistance, but is also robust against the noises caused by uncertainty and measurements.     

Microbial Power‐Generating Capabilities on Micro‐/Nano‐Structured Anodes in Micro‐Sized Microbial Fuel Cells

Microbial fuel cells (MFCs) are an alternative electricity generating technology and efficient method for removing organic material from wastewater. Their low power densities, however, hinder practical applications. A primary limitation in these systems is the anode. The chemical makeup and surface area of the anode influences bacterial respiration rates and in turn, electricity generation. Some of the highest power densities have been reported using large surface area anodes, but due to variable chemical/physical factors (e.g., solution chemistry, architecture) among these studies, meaningful comparisons are difficult to make. In this work, we compare under identical conditions six micro/nano‐structured anodes in micro‐sized MFCs (47 μL). The six materials investigated include carbon nanotube (CNT), carbon nanofiber (CNF), gold/poly (ϵ‐caprolactone) microfiber (GPM), gold/poly(ϵ‐caprolactone) nanofiber (GPN), planar gold (PG), and conventional carbon paper (CP). The MFCs using three dimensional anode structures (CNT, CNF, GPM, and GPN) exhibited lower internal resistances than the macroscopic CP and two‐dimensional PG anodes. However, those novel anode materials suffered from major issues such as high activation loss and instability for long‐term operation, causing an enduring problem in creating widespread commercial MFC applications. The reported work provides an in‐depth understanding of the interplay between micro‐/nano‐structured anodes and active microbial biofilm, suggesting future directions of those novel anode materials for MFC technologies.     

Investigation of the Ethanol Electro‐Oxidation in Alkaline Membrane Electrode Assembly by Differential Electrochemical Mass Spectrometry

The fuel cell differential electrochemical mass spectrometry (FC‐DEMS) measurements were performed for studying the ethanol oxidation reaction (EOR), using alkaline membrane electrode assemblies (MEAs) made up of nanoparticle Pt catalyst and alkaline polymeric membranes. The obtained results indicate that in an alkaline medium, ethanol undergoes significantly more complete electro‐oxidation to CO₂ than in an acidic MEA using the same Pt anode. The CO₂ current efficiency (CCE) can be compared for acidic and alkaline MEA with similar electrochemical active area on the anode side. The CCE estimated, in case of alkaline MEA with Pt anode, is around 55% at 0.8 V/RHE, 60 °C and 0.1 M ethanol. In comparison, under similar conditions, acidic MEAs using the same anode catalyst show only 2% CCE. This might indicate that the C–C bond scission rates are much higher in alkaline media. However, the mechanism of ethanol oxidation in alkaline media is not exactly known. CO₂ produced in electrochemical reaction forms soluble carbonates in the presence of aqueous alkaline electrolyte. This makes it difficult to study ethanol oxidation in alkaline media using FTIR or model DEMS systems. The alkaline polymer electrolyte membranes as used in this study for making alkaline MEAs provide an important opportunity to observe CO₂ produced during EOR using FC‐DEMS system.     

Characterization of Membrane Electrode Assemblies for High‐Temperature PEM Fuel Cells

This paper will present the characterization of two types of membrane‐electrode‐assemblies (MEAs) for high‐temperature polymer electrolyte membrane fuel cells (HT‐PEMFC) working under reformate stream. The important aspects to be considered in the characterization of these MEAs are: (i) presence of contaminants, and (ii) composition of the anode. Start/stop cycling test were performed for two different Dapozol® MEAs using different GDL materials, using first hydrogen and then synthetic reformate as a fuel gas, both with a dew point of 80 °C. With these results the influence of contaminants present in the reformate was compared for the two types of MEAs, showing the superior performance of the Dapozol® 101 MEA under these conditions. The possibility to further enhance the MEAs' resilience against the operation of reformates by changing the anode catalyst composition was evaluated in a half MEA configuration, considering that the impact of the H₂S present in the fuel presents a major issue. For this reason the hydrogen oxidation reaction (HOR) was evaluated for two types of Pt‐based electrocatalysts in an anodic half MEA configuration using different hydrogen‐rich fuel mixtures. These results provide valuable information for the optimization of the MEA and the anode catalyst for HT‐PEMFC.     

Investigation of a Novel Catalyst Coated Membrane Method to Prepare Low‐Platinum‐Loading Membrane Electrode Assemblies for PEMFCs

In this work, a novel catalyst coated membrane (CCM) approach–a catalyst‐sprayed membrane under irradiation (CSMUI)–was developed to prepare MEAs for proton exchange membrane fuel cell (PEMFC) application. Catalyst ink was sprayed directly onto the membrane and an infrared light was used simultaneously to evaporate the solvents. The resultant MEAs prepared by this method yielded very high performance. Based on this approach, the preparation of low‐platinum‐content MEAs was investigated. It was found that for the anode, even if the platinum loading was decreased from 0.2 to 0.03 mg cm^–2, only a very small performance decrease was observed; for the cathode, when the platinum loading was decreased from 0.3 to 0.15 mg cm^–2, just a 5% decrease was detected at 0.7 V, but a 35% decrease was observed when the loading was decreased from 0.15 to 0.06 mg cm^–2. These results indicate that this approach is much better than the catalyst coated gas diffusion layer (GDL) method, especially for the preparation of low‐platinum‐content MEAs. SEM and EIS measurements indicated ample interfacial contact between the catalyst layer and the membrane.     

Robust Optimal Operation of Two‐Chamber Microbial Fuel Cell System Under Uncertainty: A Stochastic Simulation Based Multi‐Objective Genetic Algorithm Approach

This investigation is performed to study the optimal operation decision of two‐chamber microbial fuel cell (MFC) system under uncertainty. To gain insight into the mechanism of uncertainty propagation, a Quasi‐Monte Carlo method‐based stochastic analysis is conducted not only to elucidate the effect of each uncertain parameter on the variability of power density output, but also to illustrate the interactive effects of the all uncertain parameters on the performance of MFC. Moreover, a systematic stochastic simulation‐based multi‐objective genetic algorithm framework is proposed to identify a set of Pareto‐optimal robust operation strategies, which is helpful to provide an imperative insight into the relationship between the mean and standard deviation of output power density. The results indicate that (1) the coefficient of variance (COV) value of output power density has a linear relationship with the COV value of each uncertainty parameter as well as all interactive parameters; and (2) a significant performance improvement with respect to both mean and standard deviation of power density is observed by implementing the multi‐objective robust optimization. These results thus validate that the proposed uncertainty analysis and robust optimization framework provide a promising tool for robust optimal design and operation of fuel cell systems under uncertainty.     

Doped Germanate‐Based Apatites as Electrolyte for Use in Solid Oxide Fuel Cells

Apatite ceramics, known for their good electrical conductivities, have garnered substantial attention as an alternative electrolyte for solid oxide fuel cells (SOFCs). However, studies focusing on the electrochemical performances of SOFCs with apatities as electrolytes remain rare, partly due to their high sintering temperature. In this study, the effects of Mg²⁺, Al³⁺, Ga³⁺, and Sn⁴⁺ dopants on the characteristics of La_9.5Ge₆O_{26 ± δ} are examined and their potential for use as SOFC electrolytes evaluated. The results indicate that La_9.5Ge_5.5Al_0.5O₂₆ is stabilized into a hexagonal structure, while the La_9.5Ge_5.5Sn_0.5O_26.25, La_9.5Ge_5.5Ga_0.5O₂₆, and La_9.5Ge_5.5Mg_0.5O_25.75 ceramics reveal triclinic cells accompanied with the second phase La₂Sn₂O₇ or La₂GeO₅. The study further demonstrates that a high sintering temperature is needed for both the La_9.5Ge_5.5Mg_0.5O_25.75 and the La_9.5Ge_5.5Sn_0.5O_26.25 ceramics, and the worst electrical conductivity among the examined systems appears in the La_9.5Ge_5.5Ga_0.5O₂₆ ceramic. The La_9.5Ge_5.5Al_0.5O₂₆ ceramic is accordingly selected for cell evaluation due to its ability to reach densification at 1,350 °C, its good electrical conductivity of 0.026 S cm^–1 at 800 °C, and its acceptable thermal expansion coefficient of 10.1 × 10^–6 K^–1. The maximum power densities of the NiO‐SDC/La_9.5Ge_5.5Al_0.5O₂₆/LSCF‐SDC single cell are found to be respectively 0.22, 0.16, 0.11, and 0.07 W cm^–2 at 950, 900, 850, and 800 °C.     

Comparative Study of On‐Line Membrane Electrode Assembly Activation Procedures in Proton Exchange Membrane Fuel Cell

The major objectives of this study are to identify the best activation procedure between commonly used procedures that can significantly reduce the conditioning duration and to understand the change in interfacial properties during conditioning. In order to do that, three on‐line activation procedures were employed for activating of identical MEAs in PEMFC and studied by polarization curve and electrochemical impedance spectroscopy (EIS). These methods are constant current (0.25 A cm^–2) for 19 h, constant voltage (0.6 V) for 9 h, and USFCC protocol. The best performance was achieved by USFCC protocol within 15 h, but by constant voltage procedure, 96% of mentioned protocol was obtained during 6 h. So constant voltage activation proceeded remarkably fast, and most of the activation process was achieved in the first few hours. Obtained results from Nyquist plots during/after MEA conditioning indicate mentioned process are irreversible and interfacial structures of MEAs are different even after finishing of MEA break‐in. It could be affected the MEA performance and even its durability. These results are consistence with the obtained performance of activated MEAs either in H₂/air or H₂/O₂ PEMFC. We found the mentioned constant current procedure consume long time without reaching to expectable performance even after 19 h.     

Membrane Electrode Assembly with Ultra Low Platinum Loading for Cathode Electrode of PEM Fuel Cell by Using Sputter Deposition

Cathode electrodes of proton exchange membrane fuel cells were fabricated by using Pt sputter deposition to increase the gravimetric power density (W mg_Pt⁻¹) with reduced Pt loading. Ultra low Pt‐based electrodes having Pt loading in between 0.0011 and 0.06 mg_Pt cm⁻² were prepared by a radio frequency (RF) sputter deposition method on the surface of a non‐catalyzed gas diffusion layer (GDL) substrate by changing the sputtering time (20, 90, 180, 1050 s). The effect of cathode Pt loading on the performance of membrane electrode assembly were investigated using polarization curve, impedance, H₂ crossover and cyclic voltammetry techniques. The effect of backpressure on PEMFC performance was also investigated. Sputter1050 (0.06 mg_Pt cm⁻²) exhibited the best power density at 80 °C cell temperature and without backpressure for H₂/O₂, 100 %RH (297 mW cm⁻² and 5 W mg_Pt⁻¹ at 0.6 V). On the other hand sputter90 (0.005 mg_Pt cm⁻²) showed the peak gravimetric power density (15 W mg_Pt⁻¹ and 75 mW cm⁻² at 0.6 V). The Pt utilization efficiency increased as the Pt loading decreased. Sputter20 and sputter90 electrodes yielded insufficient electrochemical surface area (ECSA), higher charge transfer and ohmic resistance, but sputter180 and sputter1050 yielded sufficient ECSA and lower charge transfer and ohmic resistance.     

Characterization of a Cu‐La0.75Sr0.25Cr0.5Mn0.5O3 ‐CeO2/La0.75Sr0.25Cr0.5Mn0.5O3‐YSZ/Ni‐ScSZ Three‐Layer Structure Anode in Thin Film Solid Oxide Fuel Cell Running on Methane Fuel

Anodes for Solid Oxide Fuel Cell that is capable of directly using hydrocarbon without external reforming have been of great interest recently. In this paper, a three‐layer structure anode running on methane is fabricated by tape casting and screen printing method. The slurry of catalyst layer Cu‐LSCM‐CeO₂ (with weight ratios of 1.5:7.0:1.5, 2.0:7.0:1.0, 2.15:7.0:0.85 and 2.25:7.0:0.75, weight ratios of Cu/CeO₂ is 1:1, 2:1, 2.5:1 and 3:1, respectively) is screen‐printed on LSCM‐YSZ support layer and Ni‐ScSZ active layer. Thus, LSCM‐YSZ/Ni‐ScSZ anodes with Cu‐LSCM‐CeO₂ catalyst layer (denoted as LSCM‐YSZ1010, LSCM‐YSZ2010, LSCM‐YSZ2510 and LSCM‐YSZ3010, respectively) are obtained. Single cells with three‐layer structure anode are also fabricated and measured, of which the maximum power density reaches 491 and 670 mW cm⁻² for the cell with LSCM‐YSZ2510 anode running on methane at 750 °C and 800 °C, respectively. No significant degradation in performance has been observed after 240h of cell testing when LSCM‐YSZ2510 anode is exposed to methane at 750 °C. Very little carbon deposition is detected on the anode, suggesting that carbon deposition is limited during cell operation. Consequently, Cu‐LSCM‐CeO₂ catalyst layer on the surface of LSCM‐YSZ support layer makes it possible to have good stability for long‐term operation in methane due to very little carbon deposition.     

Modeling of Solid Oxide Fuel Cells with Particle Size and Porosity Grading in Anode Electrode

Solid oxide fuel cells (SOFCs) have the potential to meet the critical energy needs of our modern civilization and minimize the adverse environmental impacts from excessive energy consumption. They are highly efficient, clean, and can run on variety of fuel gases. However, little investigative focus has been put on optimal power output based on electrode microstructure. In this work, a complete electrode polarization model of SOFCs has been developed and utilized to analyze the performance of functionally graded anode with different particle size and porosity profiles. The model helps to understand the implications of varying the electrode microstructure from the polarization standpoint. The work identified conditions when grading can improve the cell performance and showed that grading is not always beneficial or necessary.     

Performance Improvement of Wave‐Like PEMFC Stack with Compound Membrane Electrode Assembly

The novel architecture of wave‐like proton exchange membrane fuel cell (PEMFC) stack developed in our previous work achieved peak volumetric power density and specific power of 2,715.9 W L^–1 and 2,157.9 W kg^–1, respectively. However, there still existed perforated bipolar plates and the carbon fiber gas diffusion layer (GDL) was easy to cause damage during the fabrication process of undulate membrane electrode assembles (MEAs). In the present study, sintered stainless steel fiber felt (SSSFF) was employed to work as metallic GDL (MGDL) and bipolar plates simultaneously. Compound membrane electrode assembles (CMEAs) with serpentine and interdigitated flow channels were designed and fabricated using stamping process. A single cell with CMEA was assembled in house and the output performance was evaluated systemically. The results indicated that the peak volumetric power density and specific power of wave‐like PEMFC single with CMEA are 5,764.0 W L^–1 and 4,693.5 W kg^–1 respectively. This study achieved a significant performance improvement due to the concept of CMEA and may propose a possible means to meet the DOE's 2020 technical target that volumetric power density is 2,500 W L^–1 and specific power is 2,000 W kg^–1 for stack.     

CO Tolerance of Commercial Pt and PtRu Gas Diffusion Electrodes in Polymer Electrolyte Fuel Cells

The CO tolerance of commercial Pt and PtRu anode electrodes from different suppliers (E‐Tek and Tanaka) has been examined in polymer electrolyte fuel cells (PEFC) using AC‐impedance spectroscopy along steady‐state current‐voltage curves. A simple mathematical model has been derived in order to extract important kinetic parameters for CO poisoning on different anode electrodes. The Tanaka PtRu (40:60) electrode demonstrated the best CO tolerance under the selected operating conditions. Inductive behavior in the low frequency region of the impedance spectra for the E‐Tek Pt and PtRu electrode proved to be characteristic for CO poisoning. However, the impedance spectra of the Tanaka PtRu electrode did not show any inductive behavior and its CO surface coverage, extracted by fitting the experimental data to the model, was lower than the surface CO coverage of the E‐Tek electrodes.     

Distortions in Electrochemical Impedance Spectroscopy Measurements Using 3‐Electrode Methods in SOFC. II. Effect of Electrode Activity and Relaxation Times

The 3‐electrode configuration is commonly applied to quantify the overpotential of anodes or cathodes in solid‐oxide fuel cells (SOFC). In this type of set‐up, a reference electrode (RE) is used to isolate the potential loss of one electrode from that of the entire cell; however, erroneous results can be obtained whenever the RE does not precisely separate the potential drop between the two active electrodes. In this study, we present the results of a theoretical and experimental analysis focused on verifying the effectiveness of the 3‐electrode configuration in electrochemical impedance spectroscopy measurements for the kinetic characterisation of SOFC electrode reactions. The focus of this paper is on the distortion of impedance measurements caused by differences in the area‐specific polarisation resistance and impedance time constants of the working and counter electrodes. The results obtained numerically and experimentally, both for planar and tubular SOFC cell geometries, prove the reliability of the theoretical model used. From the systematic simulation presented here and in our previous work, it was possible to formulate general guidelines for the design of 3‐electrode experimental SOFC. The theoretical model used here can also be used to verify the consistency of EIS measurements obtained with thin planar cells.     

Benefits of Membrane Electrode Assemblies with Asymmetrical GDL Configurations for PEM Fuel Cells

Membrane electrode assemblies (MEAs), based on commercial catalyst‐coated membranes combined with various gas diffusion layers (GDLs) on anode and cathode, were studied in terms of their specific advantages for different operations regimes of proton exchange membrane fuel cells (PEMFCs.) It is verified that MEAs with optimized gas diffusion layer designs (backing and micro‐porous layers) on anode and cathode are able to provide improved cell performance combined with a largely reduced sensitivity towards changes in the relative humidity as compared to MEAs with symmetrical gas diffusion layer configuration.     

Distortions in Electrochemical Impedance Spectroscopy Measurements Using 3‐Electrode Methods in SOFC. I – Effect of Cell Geometry

The use of a reference electrode (RE) is necessary to independently measure the overpotential of each electrode in solid oxide fuel cells (SOFC). This type of set‐up, known as the 3‐electrode (or 3‐terminal) configuration, can give erroneous results if the RE does not effectively separate the potential of the two active electrodes. In this work, calculations and experiments were performed to verify the effectiveness of the 3‐electrode configuration used in electrochemical impedance spectroscopy (EIS) measurements for studying the kinetics of anodes and cathodes in SOFC. Initially, a theoretical analysis of the impedance distortions in relation to the electrode geometry and configuration is presented and the main causes of distortions are elucidated. Then, this analysis is corroborated by experimental results obtained using two specially designed cells. Calculations and experiments reconfirm that configurations characterised by electrodes of equal area and symmetrical placement do not produce EIS distortions when the electrodes have similar area‐specific polarisation resistances and time constants. Moreover, distortions can be low even in considerably misaligned configurations when electrodes are small and relatively inactive.     

Membrane Design for Direct Ethanol Fuel Cells: A Hybrid Proton‐Conducting Interpenetrating Polymer Network

A series of hybrid proton‐conducting membranes with an interpenetrating polymer network (IPN) structure was designed with the direct ethanol fuel cell (DEFC) application in mind. In these membranes, glutaraldehyde crosslinked poly(vinyl alcohol) (PVA) were interpenetrated with the copolymer of 2‐acrylamido‐2‐methyl‐propanesulphonic acid (AMPS) and 2‐hydroxyethyl methacrylate (HEMA) crosslinked by poly(ethylene glycol) dimethacrylate (PEGDMA). Silica from the in situ sol–gel hydrolysis of tetraethyl orthosilicate (TEOS) was uniformly dispersed in the polymer matrix. The membranes fabricated as such had ion exchange capacities of 0.84–1.43 meq g^–1 and proton conductivities of 0.02–0.11 S cm^–1. The membranes exhibited significantly lower fuel permeabilities than that of Nafion. In a manner totally unlike Nafion, fuel permeabilities were lower at higher fuel concentrations, and were lower in ethanol than methanol solutions. These behaviours are all relatable to the unique swelling characteristics of PVA (no swelling in ethanol, partial swelling in methanol and extensive swelling in water) and to the fuel blocking and swelling suppression properties of silica particles. The membranes are promising for DEFC applications since a high concentration of fuel may be used to reduce fuel crossover and to improve the anode kinetics for a resultant increase in both the energy and power densities of the fuel cell.     

Study of a Single‐Chamber Solid Oxide Fuel Cell Microstack with V‐Shaped Congener‐Electrode‐Facing Configuration

Single‐chamber solid oxide fuel cell (SC‐SOFC) microstacks with V‐Shaped congener‐electrode‐facing configuration were fabricated and operated successfully in a box‐like stainless steel chamber. Two gas channels with small gas inlets were used to transport the fuel and oxygen to the anodes and cathodes, respectively. The temperature of an anode‐facing‐anode two‐cell stack was higher than that of a cathode‐facing‐cathode two‐cell stack during the test procedure. For a three‐cell stack, the cell in the middle region presented the highest power output. The open circuit voltage (OCV) and maximum power output of the three‐cell stack in a gas mixture of 100 sccm N₂, 120 sccm CH₄, and 80 sccm O₂ were 3.0 V and 413 mW, respectively.