A direct carbon fuel cell with (molten carbonate)/(doped ceria) composite electrolyte

A composite electrolyte containing a Li/Na carbonate eutectic and a doped ceria phase is employed in a direct carbon fuel cell (DCFC). A four-layer pellet cell, viz. cathode current collector (silver powder), cathode (lithiated NiO/electrolyte), electrolyte and anode current collector layers (silver powder), is fabricated by a co-pressing and sintering technique. Activated carbon powder is mixed with the composite electrolyte and is retained in the anode cavity above the anode current collector. The performance of the single cell with variation of cathode gas and temperature is examined. With a suitable CO₂/O₂ ratio of the cathode gas, an operating temperature of 700 °C, a power output of 100 mW cm⁻² at a current density of 200 mA cm⁻² is obtained. A mechanism of O²⁻ and CO₃²⁻ binary ionic conduction and the anode electrochemical process is discussed.     

A novel cathode structure with double catalyst layers and low Pt loading for proton exchange membrane fuel cells

A novel cathode structure (NCS) was developed, which consisted of an inner and an outer catalyst layer (CL). It showed an improved platinum (Pt) utilization (above 50%), a lowered CL/gas diffusion layer interfacial resistance, and a decreased mass transport polarization compared with the traditional cathode structure (TCS). A hydrogen/air proton exchange membrane fuel cell employing NCS yielded an output power density up to 0.76 W cm⁻² with cathode Pt loading as low as 0.28 mg cm⁻². The enhanced performance of NCS is attributed to synergistic effect of the two catalyst supports in outer CL, which provides abundant pores to relieve water flooding and facilitates heat-induced proton conductor migration from the inner to outer CL, forming a hydrophilic proton conduction network. Moreover, the thin and compact inner CL can meet the demand of rich active sites and catalyst migration toward the regions nearest to the membrane under high current densities.     

Pt nanowire growth induced by Pt nanoparticles in application of the cathodes for Polymer Electrolyte Membrane Fuel Cells (PEMFCs)

Improving cathode performance at a lower Pt loading is critical in commercial PEMFC applications. A novel Pt nanowire (Pt-NW) cathode was developed by in-situ growth of Pt nanowires in carbon matrix consisting Pt nanoparticles (Pt-NPs). Characterization of TEM and XRD shows that the pre-existing Pt-NPs from Pt/C affect Pt-NW morphology and crystallinity and Pt profile crossing the matrix thickness. The cathode with Pt-NP loading of 0.005 mg_Pt-NP cm^?2 and total cathode Pt loading of 0.205 mg_Pt cm^?2 has the specific current density of 89.56 A g_Pt^?1 at 0.9 V, which is about 110% higher than that of 42.58 A g_Pt^?1 of the commercial gas diffusion layer (GDE) with Pt loading of 0.40 mg cm^?2. When cell voltage is below 0.48 V, the Pt-NW cathode has better performance than the commercial GDE. It is believed that the excellent performance of the Pt-NW cathode is attributed to Pt-NP induction, therefore producing unique Pt-NW structure and efficient Pt utilization. A Pt-NW growth mechanism was proposed that Pt precursor diffuses into the matrix consisting of pre-existent Pt-NPs by concentration driving, and Pt-NPs provide priority sites for platinum depositing at early stage and facilitate Pt-NW growth.     

Effects of gas diffusion layer (GDL) and micro porous layer (MPL) on cathode performance in microbial fuel cells (MFCs)

This study focused on novel cathode structures to increase power generation and organic substrate removal in microbial fuel cells (MFCs). Three types of cathode structures, including two-layer (gas diffusion layer (GDL) and catalyst layer (CL)), three-layer (GDL, micro porous layer (MPL) and CL), and multi-layer (GDL, CL, carbon based layer (CBL) and hydrophobic layers) structures were examined and compared in single-chamber MFCs (SCMFCs). The results showed that the three-layer (3L) cathode structures had lower water loss than other cathodes and had a high power density (501 mW/m²). The MPL in the 3L cathode structure prevented biofilm penetration into the cathode structure, which facilitated the oxygen reduction reaction (ORR) at the cathode. The SCMFCs with the 3L cathodes had a low ohmic resistance (R_ohmic: 26-34 Ω) and a high cathode open circuit potential (OCP: 191 mV). The organic substrate removal efficiency (71-78%) in the SCMFCs with 3L cathodes was higher than the SCMFCs with two-layer and multi-layer cathodes (49-68%). This study demonstrated that inserting the MPL between CL and GDL substantially enhanced the overall electrical conduction, power generation and organic substrate removal in MFCs by reducing water loss and preventing biofilm infiltration into the cathode structure.     

Combined micro-scale and macro-scale modeling of the composite electrode of a solid oxide fuel cell

The design of a cathode inter-layer is important to the high performance of a solid oxide fuel cell (SOFC). In this paper, the processes of electrochemical reactions, electronic and ionic conductions and gas transports in an SOFC are discussed in detail. An analysis shows that the current conduction and electrochemical processes can be replicated by an equivalent circuit model. A corresponding macro-scale model using the Butler-Volmer equation for electrochemical reactions, Ohm's law for current conduction and the Dusty-gas model for gas transport is described. A percolation theory based micro-model is used to obtain the effective electrode properties in the macro-model from the microstructure parameters of the porous electrode. Experimental I-V relations can be accurately accounted for by the proposed theory. The macro- and micro-models are then combined to systematically examine the effects of various parameters on the performance of a composite cathode inter-layer. The examined parameters include the thickness, effective electronic and ionic conductivities, exchange current density, operating temperature, output current density, electrode- and electrolyte-particle radii, composition and porosity of the cathode inter-layer. The comprehensive study shows conclusively that a cathode inter-layer thickness in a range of 10-20 μm is optimal for all practical material choices and microstructure designs.     

Carbon-coated fluorinated graphite for high energy and high power densities primary lithium batteries

The electrochemical performances of fluorinated graphite have been improved by coating a uniform carbon layer on commercial CF_x (x = 1) powder used as cathode material in lithium battery. In comparison with the cell using un-coated CF_x as cathode, the cell using carbon coated CF_x cathode has a higher energy density and higher power density, particularly at higher discharge current rates (1C above). This is because the conductive carbon coating provides the exterior connectivity between particles for facile electron conduction, resulting in high rate performance.     

Effects of chlorides on the performance of proton exchange membrane fuel cells

This paper investigates the effects of cathode gases containing chloride ions on the proton exchange membrane fuel cell (PEMFC) performance. Chloride solutions are vaporized using an ultrasonic oscillator and mixed with oxygen/air. The salt concentration of the mixed gas in the cathode is set by varying the concentration of the chloride solution. Five-hour tests show that an increase in the concentration of sodium chloride did not significantly affect the cell performance of the PEMFC. It is found that variations in the concentration of chloride do not show significant influence on the cell performance at low current density operating condition. However, for high current density operating conditions and high calcium chloride concentrations, the chloride ion appears to have a considerable effect on cell performance. Experimental results of 108-h tests indicate that the fuel cell operating with air containing calcium chloride has a performance decay rate of 3.446 mV h⁻¹ under the operating condition of current density at 1 A/cm². From the measurements of the I-V polarization curves, it appears that the presence of calcium chloride in the cathode fuel gas affects the cell performance more than sodium chloride does.     

Electrochemical reduction of silver vanadium phosphorous oxide, Ag2VO2PO4: Silver metal deposition and associated increase in electrical conductivity

This report details the chemical and associated electrical resistance changes of silver vanadium phosphorous oxide (Ag₂VO₂PO₄, SVPO) incurred during electrochemical reduction in a lithium based electrochemical cell over the range of 0-4 electrons per formula unit. Specifically the cathode electrical conductivities and associated cell DC resistance and cell AC impedance values vary with the level of reduction, due the changes of the SVPO cathode. Initially, Ag⁺ is reduced to Ag⁰ (2 electrons per formula unit or 50% of the calculated theoretical value of 4 electrons per formula unit) accompanied by significant decreases in the cathode electrical resistance, consistent with the formation of an electrically conductive silver metal matrix within the SVPO cathode. As Ag⁺ reduction progresses, V⁵⁺ reduction initiates; once the SVPO reduction process progresses to where the reduction of V⁵⁺ to V⁴⁺ is the dominant process, both the cell and the cathode electrical resistances then begin to increase. If the discharge then continues to where the dominant cathode reduction process is the reduction of V⁴⁺ to V³⁺, the cathode and cell electrical resistances then begin to decrease. The complex cathode electrical resistance pattern exhibited during full cell discharge is an important subject of this study.     

Proton exchange membrane (PEM) electrolyzer operation under anode liquid and cathode vapor feed configurations

Proton exchange membrane (PEM) electrolysis is a potential alternative technology to crack water in specialty applications where a dry gas stream is needed, such as isotope production. One design proposal is to feed the cathode of the electrolyzer with vapor phase water. This feed configuration would allow isotopic water to be isolated on the cathode side of the electrolyzer and the isotope recovery system could be operated in a closed loop. Tests were performed to characterize the difference in the current–voltage behavior between a PEM electrolyzer operated with a cathode water vapor feed and with an anode liquid water feed. The cathode water vapor feed cell had a maximum limiting current density of 400 mA/cm² at 70 °C compared to a current density of 800 mA/cm² for the anode liquid feed cell at 70 °C. The limiting current densities for the cathode water vapor feed cell were similar to those predicted by a water mass transfer model. It is estimated that a cathode water vapor feed electrolyzer system will need to be between 5 and 8 times larger in active area or number of cells than an anode liquid feed system.     

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.     

DC conduction mechanism in polyvinyl alcohol films doped with potassium thiocyanate

The current–voltage characteristics of pure polyvinyl alcohol (PVA) films and those doped with potassium thiocyanate (KSCN) are studied as a function of film temperature and dopant concentration. The conduction mechanisms operative in the films in different temperature and voltage ranges are estimated from the behaviour of log I versus V^1/2 plots (I=current, V=voltage). For undoped (pure) films, the conduction mechanism appears to be essentially a Schottky type. On doping, there is considerable influence on the type of conduction mechanism, especially at lower temperatures. At higher temperatures, however, there is no significant effect of doping on the conduction mechanism.     

Pressurized PEM water electrolysis: Dynamic modelling focusing on the cathode side

This paper describes a lumped dynamic model for a high pressure PEM water electrolyzer. Since the electrolyzer under analysis is characterized by unbalanced pressure configuration with high cathodic working pressure, the model focuses on the cathode side to adequately predict the electrolyzer performance, analyzing and highlighting the importance of the cathodic activation overpotential term. The model is calibrated using experimental data from a 5.6 kW PEM water electrolyzer stack. A very good fit can be observed between the model and the experimental data, not only at different temperatures, but also at different pressures. It is found that the rise of temperature affects mainly the ohmic overpotential, while increasing the cathode pressure leads to an increment in the cathode activation overpotential that is not negligible for the electrolyzer performance. By rising the operating current, the cathode activation overpotential becomes 63% of that of the anode (at 70 bar, 1.2 A/cm² and 50 °C).     

Intermediate temperature fuel cell with a doped ceria-carbonate composite electrolyte

The performance of a composite electrolyte composed of a samarium doped ceria (SDC) and a binary eutectic carbonate melt phase has been examined. This material shows higher ionic conductivity than pure SDC in intermediate temperature region. SDC with different morphologies is obtained by co-precipitation, sol-gel and glycine-nitrate combustion preparation techniques. A tri-layer single cell is prepared with a cost-effective co-pressing and co-sintering technique. It is found that the surface properties of SDC and the electrolyte thickness have a great influence on the fuel cell performance. When the co-precipitated SDC is used as the electrolyte component and CO₂/O₂ gas mixture is adopted as the cathode oxidant gas, a fuel cell with an excellent performance is obtained, which has a peak power output of 1704 mW cm⁻² at a current density of 3000 mA cm⁻² at 650 °C. The influence of cathode atmosphere is examined with conductivity measurement and fuel cell performance test. The results support the concept of O²⁻/H⁺/CO₃²⁻ ternary conduction.     

Impact of channel geometry on two-phase flow in fuel cell microchannels

An important function of the gas delivery channels in PEM fuel cells is the evacuation of water at the cathode. The resulting two-phase flow impedes reactant transport and causes parasitic losses. There is a need for research on two-phase flow in channels in which the phase fraction varies along the flow direction as in operating fuel cells. This work studies two-phase flow in 60 cm long channels with distributed water injection through a porous GDL wall to examine the physics of flows relevant to fuel cells. Flow regime maps based on local gas and liquid flow rates are constructed for experimental conditions corresponding to current densities between 0.5 and 2 A cm⁻² and stoichiometric coefficients from 1 to 4. Flow structures transition along the length of the channel. Stratified flow occurs at high liquid flow rates, while intermittent slug flow occurs at low liquid flow rates. The prevalence of stratified flow in these serpentine channels is discussed in relation to water removal mechanisms in the cathode channels of PEM fuel cells. Corners facilitate formation of liquid films in the channel, but may reduce the water-evacuation capability. This analysis informs design guidelines for gas delivery microchannels for fuel cells.     

The influence of gas diffusion layer wettability on direct methanol fuel cell performance: A combined local current distribution and high resolution neutron radiography study

The influence of the anode and cathode GDL wettability on the current and media distribution was studied using combined in situ high resolution neutron radiography and locally resolved current distribution measurements. MEAs were prepared by vertically splitting either the anode or cathode carbon cloth into a less hydrophobic part (untreated carbon cloth ‘as received’) and a more hydrophobic part (carbon cloth impregnated by PTFE dispersion). Both parts were placed side by side to obtain a complete electrode and hot-pressed with a Nafion membrane. MEAs with partitioned anode carbon cloth revealed no difference between the untreated and the hydrophobised part of the cell concerning the fluid and current distribution. The power generation of both parts was almost equal and the cell performance was similar to that of an undivided MEA (110 mW cm⁻², 300 mA cm⁻², 70 °C). In contrast, MEAs with partitioned cathode carbon cloth showed a better performance for the hydrophobised part, which contributed to about 60% of the overall power generation. This is explained by facilitated oxygen transport especially in the hydrophobised part of the cathode gas diffusion layer. At an average current density of 300 mA cm⁻², a pronounced flooding of the cathode flow field channels adjacent to the untreated part of GDL led to a further loss of performance in this part of the cell. The low power density of the untreated part caused a significant loss of cell performance, which amounted to less than 40 mW cm⁻² (at 300 mA cm⁻²).     

Preparation and performance of a nano-honeycomb cathode for microtubular solid oxide fuel cells

The effect of a nano-honeycomb cathode on the performance of a microtubular solid oxide fuel cell is investigated. We successfully prepared nano-honeycomb cathodes with high unsealing pore porosity (～64.6%) and high structural strength by freeze casting, which improved the adsorption and dissociation of oxygen. We added gadolinium doped ceria (GDC) nanopowder to the lanthanum strontium cobalt ferrite (LSCF) cathode material. The cell performance of the nano-cell structure of the GDC-LSCF cathode is significantly improved compared to a traditional GDC-LSCF cathode with a spongy porous structure. At 750 °C, the current density is 1450 mA cm^?2 and the power density is 475 mW cm^?2, which is better than that of conventional cathode structures. We discussed the effects of the honeycomb structure on the cell, including the migration of silver paste as a cathodic collector to the GDC-LSCF interface and the improvement of the activity of the oxygen electrodes.     

Control of self-organization of drop-casted Nafion film for improving proton conduction in a polymer-electrolyte-membrane fuel cell to raise its output power density

A simple drop-cast method to directly deposit Nafion polymer electrolyte membrane (PEM) on nanostructured thin-film catalyst layer composed of stacked Pt nanoparticles prepared by pulsed laser deposition (PLD) was demonstrated. Through optimization of solvent composition and drying temperature of Nafion solution to control self-organization of Nafion, a uniform PEM with better bulk and interface microstructures could be produced, leading to a significant improvement in the output current density of a PEM fuel cell over that using reference commercial PEMs. The formation of facile proton conduction pathways in the bulk Nafion membrane resulted in a 35% reduction in ohmic resistance compared to that with the commercial membrane. Moreover, the infiltration of Nafion in the catalyst layer formed suitable proton transport network to render more catalyst nanoparticles effective and thus lower charge-transfer resistance. With the optimized PLD, drop-cast, and hot-pressing conditions, the current density of PEMFCs using drop-casted PEM reached 1902 mA cm⁻² at 0.6 V at 2 atm H₂ and O₂ pressures with a cathode Pt loading of 100 μg cm⁻², corresponding to a power density of 1.14 W cm⁻² and a cathode mass-specific power density of 11.4 kW g⁻¹.     

Recovery of hydrogen from hydrogen sulfide by indirect electrolysis process

Recovery hydrogen from hydrogen sulfide is an effective way of utilizing exhaust gas. In this paper, removal of hydrogen sulfide by indirect electrochemical process was studied using acidic aqueous solution of Fe³⁺/Fe²⁺ as the electrochemical intermediate. Solid polymer electrolyte was applied to hydrogen production by indirect electrolysis of H₂S, in which the anode was graphite cloth, the cathode was the platinized graphite cloth, and the membrane was proton exchange membrane. The results of electrolysis experiments showed the relationship of current density as a function of electrolytic voltage at constant flow rate of electrolyte, temperature, and electrolyte composition. The effect of the cathode liquid velocity on current density was small. When the flow rate of anode electrolyte was greater than 200 L/hr., the current density tended to be stable. When [Fe³⁺]>0.20 mol/L, the concentrations of Fe²⁺ and Fe³⁺ ions in the anode solution had no significant impact on the current density. The current density gradually increased with temperature. In the electrolytic process of hydrogen production, the Fe²⁺ ions diffused from the anode to the cathode. The amount of diffusing Fe²⁺ ions gradually increased with time. The effect of Fe²⁺ ions diffusion from anode to cathode on hydrogen production was discussed.     

Local current density and water management in PEMFCs

We have used computational fluid dynamics analysis to investigate the local current density distribution at the membrane-gas diffusion layer (GDL) interface at average current densities ranging from 0.1 to 2.4 A/cm². A three-dimensional, non-isothermal model was used with a single straight channel geometry. Both anode and cathode humidification were included in the model. In addition, phase transportation was included in the model to predict the distributions of water vapor and liquid water and the related water management for systems operating at different current densities. The dependency of local current density on total water and thermal management of the fuel cell and its other related linkage with physical parameters were investigated. The simulation results showed that at low average current density, the local current density does not vary along the width but gradually decreases along the cell length. However, the opposite trend starts to emerge as the average current density is increased. The anode water activity was found to play a significant role in determining the membrane conductivity and the local current density variation in the cell. Moreover, at high average current density, the local current density in the downstream end of the channel is dominated by the cathode water rather than the membrane conductivity. Specifically, the cathode water accumulates in the shoulder area and congests the pores of the GDL, thereby blocking the passage of oxygen to the reacting area. The resulting scarcity of oxygen in the shoulder area causes a dramatic reduction in the local current density in this region. Simulations using different cathode stoichiometric rates showed that increasing the cathode stoichiometric rate led to better oxygen transportation to the GDL at the shoulder area, and hence improved to smooth the local current density distribution. The model was validated by comparison with the polarization curve (I–V characteristics) in the literature.     

Current density effect on hydrogen permeation in PEM water electrolyzers

Hydrogen permeation is an important phenomena for PEM water electrolyzers, due to several reasons as safety issues and efficiency loss. The present contribution deals with the measurement of hydrogen volume fraction within the anode product gas during PEM water electrolysis for different temperatures and cathode pressures. High cathode pressures lead to high anode hydrogen volume fractions close to the lower explosion limit of hydrogen in oxygen, which are caused by increased hydrogen permeation. It is shown that the results of the hydrogen volume fraction measurements can be easily converted into hydrogen permeation rates. Additionally, the experimental obtained permeation data indicate that hydrogen permeation increases linear with increasing current density. The impact of current density on the hydrogen permeation is very strong in comparison to the effects of temperature and pressure e.g. a current density increase of 1 A/cm² can causes a permeation increase comparable to a cathode pressure increase of 20 bar. In the second part of this contribution different theories to explain this strong dependence on current density are discussed. The most probable explanation is that due to mass transfer limitations a supersaturation of dissolved gas within the catalyst ionomer film arises that causes the investigated increase in permeation.