Feasibility of using ash-free coal in a solid-oxide-electrolyte direct carbon fuel cell

The feasibility of using ash-free coal as the fuel in a direct carbon fuel cell (DCFC) was investigated. Tubular-electrolyte-supported single cells were operated at high temperatures with continuous fuel feeding equipment. A single cell consisted of an yttria-stabilized zirconia (YSZ) electrolyte tube support, a NiO-YSZ cermet anode, and an LSM-YSZ composite cathode. The solvent extraction method was used to remove mineral matter and ash from raw coal. From thermal gravimetric analysis, the ash content of the ash-free coal was found to be nearly zero, but its volatile matter content was 38.34 wt.%. Scanning electron microscopy (SEM) observations and visualization tests were carried out for characterization of the interface of the ash-free coal; the results showed that the ash-free coal was in a liquid-like phase at high temperatures because the volatile matter in the coal produced by solvent extraction could help maintain carbon in the liquid-like state on the anode at high temperatures. The cell performance was affected by this liquid-like state at high temperatures.     

Enhancement of electrooxidation activity of activated carbon for direct carbon fuel cell

Direct carbon fuel cells are promising power sources using solid carbon directly as fuel. Their performances significantly depend on the electrooxidation activity of carbon fuel. Electrooxidation of activated carbon particulates in molten Li₂CO₃–K₂CO₃ was investigated by potentiodynamic and potentiostatic method. Results indicated that the electrooxidation performance of activated carbon was significantly enhanced by pre-soaking with Li₂CO₃–K₂CO₃ and by treatment with HF, HNO₃ and NaOH, respectively. The onset potential negatively shifted by around 100 mV and the current density increased by around 50 mA cm⁻² after pre-soaking. The non-oxidant acids (HF) treatments are more effective than oxidant acid (HNO₃) and base (NaOH) treatments. HF treated activated carbon exhibited the highest activity among all the samples. The enhancement in electrooxidation performance can be closely correlated with the increase in surface area and porosity caused by acid and base treatments.     

Carbon anode in direct carbon fuel cell

Direct carbon fuel cell (DCFC) is a kind of high temperature fuel cell using carbon materials directly as anode. Electrochemical reactivity and surface property of carbon were taken into account in this paper. Four representative carbon samples were selected. The most suitable ratio of the ternary eutectic mixture Li₂CO₃–K₂CO₃–Al₂O₃ was determined at 1.05:1.2:1(mass ration). Conceptual analysis for electrochemical reactivity of carbon anode shows the importance of (1) reactive characteristics including lattice disorder, edge-carbon ratio and the number of short alkyl side chain of carbon material, which builds the prime foundation of the anodic half-cell reaction; (2) surface wetting ability, which assures the efficient contact of anode surface with electrolyte. It indicates that anode reaction rate and DCFC output can be notably improved if carbon are pre-dispersed into electrolyte before acting as anode, due to the straightway shift from cathode to anode for CO₃²⁻ provided by electrolyte soaked in carbon material.     

Performance evaluation of tubular fuel cells fuelled by pulverized graphite

A fuel cell fuelled by carbonaceous graphite is proposed. The tubular fuel cell, with the carbon in a fixed-bed form on the anode side, is employed to convert directly the chemical energy of carbon into electricity. Surface platinum electrodes are coated on the cell electrolyte, which is a yttria-stabilized zirconia (YSZ) tube of 1.5 mm thickness. The effect of using different sizes of graphite powder (in the range 0-180 μm) as fuel is analyzed. Power density and actual open-circuit voltage (OCV) values are measured as the temperature is varied from 0 to 950 °C. The cell provides a maximum power density of 16.8 mW cm⁻² and an OCV of 1.115 V at the highest temperature condition (950 °C) tested in this study.     

A novel direct carbon fuel cell by approach of tubular solid oxide fuel cells

A direct carbon fuel cell based on a conventional anode-supported tubular solid oxide fuel cell, which consisted of a NiO-YSZ anode support tube, a NiO-ScSZ anode functional layer, a ScSZ electrolyte film, and a LSM-ScSZ cathode, has been successfully achieved. It used the carbon black as fuel and oxygen as the oxidant, and a preliminary examination of the DCFC has been carried out. The cell generated an acceptable performance with the maximum power densities of 104, 75, and 47 mW cm⁻² at 850, 800, and 750 °C, respectively. These results demonstrate the feasibility for carbon directly converting to electricity in tubular solid oxide fuel cells.     

Modeling and simulation of a single direct carbon fuel cell

A mathematical model was developed to simulate the performance of a direct carbon fuel cell. The model takes account of the electrochemical reaction dynamics, mass-transfer and the electrode processes. An improved packed bed anode was adopted. Polarization losses for the cell components were examined supposing graphite as the fuel and molten carbonate as the electrolyte. The results indicated that the anode activation polarization was the major potential loss in 923–1023 K. The effects of temperature, anode dimension, and carbon particle size on the cell performance were investigated. The model predicted that the power density can be as high as 200–500 W m⁻², with carbon particle size in the range 1.0 × 10⁻⁷ to 1.0 × 10⁻⁴ m and in 923–1023 K and that the overall efficiency of the cell is higher than 55% for low current density and is 45–50% for high current density.     

Electricity generation from corn cob char though a direct carbon solid oxide fuel cell

Solid oxide fuel cell (SOFC) is a potential technology for utilizing biomass to generate electricity with high conversion efficiency and low pollution. Investigations on biomass integrated gasification SOFC system show that gasifier is one of the high cost factors which impede the practical application of such systems. Direct carbon solid oxide fuel cell (DC-SOFC) may provide a cost effective option for electricity generation from biomass because it can operate directly using biochar as the fuel so that the gasification process can be avoided. In this paper, the feasibility of using corn cob char as the fuel of a DC-SOFC to generate electricity is investigated. Electrolyte-supported SOFCs, with yttrium stabilized zirconia (YSZ) as the electrolyte, cermet of silver and gadolinium-doped ceria (GDC) as the anode and the cathode, are prepared and tested with fixed bed corn cob char as fuel and static ambient air as oxidant. The maximum power output of a DC-SOFC operated on pure corn cob char is 204 mW cm⁻² at 800 °C and it achieves 270 mW cm⁻² when Fe of 5% mass fraction, as a catalyst of the Boudouard reaction, is loaded on the corn cob char. The discharging time of the cell with 0.5 g corn cob char operated at a constant current of 0.1 A lasts 17 h, representing a fuel conversion of 38%. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and Raman spectroscopy have been applied to characterize the char-based fuels.     

Evaluation of carbon materials for use in a direct carbon fuel cell

The direct carbon fuel cell (DCFC) employs a process by which carbon is converted to electricity, without the need for combustion or gasification. The operation of the DCFC is investigated with a variety of solid carbons from several sources including some derived from coal. The highly organized carbon form, graphite, is used as the benchmark because of its availability and stability. Another carbon form, which is produced at West Virginia University (WVU), uses different mixtures of solvent extracted carbon ore (SECO) and petroleum coke. The SECO is derived from coal and both this and the petroleum coke are low in ash, sulfur, and volatiles. Compared to graphite, the SECO is a less-ordered form of carbon. In addition, GrafTech, Inc. (Cleveland, OH) supplied a well-fabricated baked carbon rod derived from petroleum coke and conventional coal–tar binder. The open-circuit voltage of the SECO rod reaches a maximum of 1.044 V while the baked and graphite rods only reach 0.972 V and 0.788 V, respectively. With this particular cell design, typical power densities were in the range of 0.02–0.08 W cm⁻², while current densities were between 30 and 230 mA cm⁻². It was found that the graphite rod provided stable operation and remained intact during multi-hour test runs. However, the baked (i.e., non-graphitized) rods failed after a few hours due to selective attack and reaction of the binder component.     

Mechanism for carbon direct electrochemical reactions in a solid oxide electrolyte direct carbon fuel cell

The carbon direct electrochemical reactions in a solid oxide electrolyte direct carbon fuel cell (DCFC) are investigated experimentally with CH₄-deposited carbon at the anode as fuel. The surface morphology of the anode cross-sections is characterized using a scanning electron microscope (SEM), the elemental distribution using an energy dispersive spectrometer (EDS) and an X-ray photoelectron spectroscopy (XPS), and the deposited carbon microstructures using a Raman spectrometer. The results indicate that all the carbon deposited on the yttrium-stabilized zirconium (YSZ) particle surfaces, the Ni particle surfaces, as well as the three-phase boundary, can participate in the electrochemical reactions during the fuel cell discharging. The direct electrochemical reactions for carbon require the two conditions that the O²⁻ in the ionic conductor contact with a carbon reactive site and that the released electrons are conducted to the external circuit. The electrochemical reactions for the deposited carbon are most difficult on the Ni particle surfaces, easier on the YSZ particle surfaces and easiest at the three-phase boundary. Not all the carbon deposited in the anode participates in the direct electrochemical reactions. The deposited carbon and the O²⁻ in the YSZ react to form the double-bonded adsorbed carbonyl group CO.     

Lignite as a fuel for direct carbon fuel cell system

Lignite, also known as brown coal, and char derived from lignite by pyrolysis were investigated as fuels for direct carbon solid oxide fuel cells (DC-SOFC). Experiments were carried out with 16 cm² active area, electrolyte supported solid oxide fuel cell (SOFC), using pulverized solid fuel directly fed to DC-SOFC anode compartment in a batch mode, fixed bed configuration. The maximum power density of 143 mW/cm² was observed with a char derived from lignite, much higher than 93 mW/cm² when operating on a lignite fuel. The cell was operating under electric load until fuel supply was almost completely exhausted. Reloading fixed lignite bed during a thermal cycle resulted in a similar initial cell performance, pointing to feasibility of fuel cell operation in a continuous fuel supply mode. The additional series of experiments were carried out in SOFC cell, in the absence of solid fuels, with (a) simulated CO/CO₂ gas mixtures in a wide range of compositions and (b) humidified hydrogen as a reference fuel composition for all cases considered. The solid oxide fuel cell, operated with 92%CO + 8%CO₂ gas mixture, generated the maximum power density of 342 mW/cm². The fuel cell performance has increased in the following order: lignite (DC-SOFC) < char derived from lignite (DC-SOFC) < CO + CO₂ gas mixture (SOFC) < humidified hydrogen (SOFC).     

Use of ash-free “Hyper-coal” as a fuel for a direct carbon fuel cell with solid oxide electrolyte

“Hyper-coal”, produced by the Kobe Steel Company, was investigated by analytical and physico-chemical methods to consider its potential usability as a fuel for a direct carbon fuel cell with solid oxide electrolyte (DC-SOFC). The performed tests showed that DC-SOFCs fed with this processed fossil coal were characterized by stable operation with reasonable current and power densities. The performance of the fuel cells can be improved by using iron as a catalyst for the anodic reaction and by the choice of appropriate working conditions.     

Review: Direct ethanol fuel cells

Direct ethanol fuel cells have attracted much attention recently in the search for alternative energy resources. As an emerging technology, direct ethanol fuel cells have many challenges that need to be addressed. Many improvements have been made to increase the performance of direct ethanol fuel cells, and there are great expectations for their potential. However, many improvements need to be made in order to enhance the potential of direct ethanol fuel cells in the future. This paper addresses the challenges and the developments of direct ethanol fuel cells at present. It also presents the applications of DEFC.     

Application of biochar derived from used cigarette filters in direct carbon solid oxide fuel cell

As a typical waste, used cigarette filters (UCFs) are difficult to biodegrade and harmful to the environment. The direct carbon solid oxide fuel cell (DC-SOFC) is an energy conversion device that can utilize carbon directly, including biochar, as fuel. We report a superior DC-SOFC powered by Fe-loaded UCF biochar in this paper. The microstructure and composition are characterized, indicating that the UCF biochar is micron-sized and contains metal elements such as K and Ca that are beneficial to the performance of DC-SOFC. The peak power density of the cell fueled by pure UCF biochar is 308 mW cm^?2 and increases to 341 mW cm^?2 after loading Fe as the catalyst, which is comparable to that of the cell with Fe-loaded activated carbon (368 mW cm^?2). It proves the feasibility of the UCF biochar as fuel for DC-SOFCs, providing a theoretical basis and technical demonstration for the disposal and transformation of solid waste.     

Performance improvement of direct carbon fuel cell by introducing catalytic gasification process

In this paper, the effects of catalytic gasification on the solid oxide electrolyte DCFC (direct carbon fuel cell) performance are experimentally investigated and analyzed using K, Ca, Ni as catalyst in carbon black and controlling the temperatures of cell and carbon black at 750 °C and 700-1000 °C, respectively. The average power densities are 976, 1473 and 1543 W m⁻² respectively for 900, 950 and 1000 °C pure carbon black gasification. Catalytic gasification improves the DCFC performance significantly. For the same performance of pure carbon black, the gasification temperatures decrease about 200, 130 and 150 °C with K, Ca and Ni additives, respectively. The catalytic effects for carbon black gasification with CO₂ are: K > Ni > Ca. For typical identical temperature DCFC operating at 750 °C, the power densities of 0.7 V discharging are 1477, 1034 and 1123 W m⁻² for the carbon black with K, Ca and Ni additives, respectively. It is possible to reduce the operation temperature of DCFC to the medium temperature range of solid oxide electrolyte (600-800 °C) by introducing catalytic gasification process.     

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.     

Effect of contact type between anode and carbonaceous fuels on direct carbon fuel cell reaction characteristics

The contact between the anode and the carbonaceous fuel has a strong effect on the direct carbon fuel cell (DCFC) reaction characteristics. These effects are experimentally investigated by measuring the electrochemical behavior of a detached anode, an anode in physical contact with the fuel and an anode with carbon deposited on the surface in a DCFC. The results show that for the detached type DCFC, the reaction characteristics are closely related to the anode gas. In an Ar atmosphere, the main anode reactions are the electrochemical reaction to produce O₂ and the carbon gasification with the formed O₂. In a CO₂ atmosphere, the main anode reactions are the carbon gasification with CO₂ and the electrochemical oxidization of the formed CO. For the physical contact type DCFC, the anode reaction mechanisms are the same as for the detached type DCFC with no electrochemical oxidization of carbon at the physical contact interface between the carbonaceous fuel and the anode. Thus, the increased contact does not result in better performance. The carbon-deposited type DCFC has better performance with a significant activation polarization due to the electrochemical oxidization of the deposited carbon.     

Analysis of the carbon anode in direct carbon conversion fuel cells

The total electrochemical efficiency of a direct carbon fuel cell with molten carbonate electrolyte is dominated by the product of coulombic efficiency (electron yield (n) per carbon atom, divided by 4) and voltaic efficiency (ratio of cell voltage to theoretical voltage). The voltaic efficiency is acceptably high (70–80%) for many atomically-disordered carbon materials. High coulombic efficiency is more difficult to achieve but ranges from below 50% at low current densities in porous material to 100% in certain monolithic and particulate carbon anodes at high current densities where substantially pure CO₂ is the product gas. We find evidence for two competing anode reactions associated with distinct low- and high polarization segments, respectively: (1) a charge-transfer controlled, linear–polarization reaction occurring predominately within pores, proportional to specific area, and tending toward low efficiency by co-production of CO and CO₂; and (2) a flow-dependent reaction occurring on the exterior surface of the anode, requiring > 100 mV polarization and tending to produce CO₂. Based on this interpretation, high electrochemical efficiency of a carbon fuel cell is expected with anodes made of atomically disordered ("turbostratic") carbon that have negligible porosity, or with anodes of disordered carbon for which interior pores are intentionally blocked with an impervious solid material, such as an inert salt or readily carbonized pitch.     

Optimization of a direct carbon fuel cell for operation below 700 °C

Direct carbon fuel cells (DCFCs) are the most efficient technology to convert solid carbon energy to electricity and thus could have a major impact on reducing fuel consumption and CO₂ emissions. The development of DCFCs to commercialisation stage is largely prohibited by their poor power densities due to the high resistive loss from anode. Here, we report a high-performance Sm_0.2Ce_0.8O_1.9 electrolyte-supported hybrid DCFC with Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ cathode and optimised anode configuration. The catalytic oxidation of carbon is improved, which results in an area specific resistance of only 0.41 Ω cm² at 650 °C at the anode. The hybrid DCFC achieves a peak power density of 113.1 mW cm⁻² at 650 °C operating on activated carbon. The stability of the fuel cell has also been improved due to the optimised current collection.     

Highly efficient utilization of industrial barium slag for carbon gasification in direct carbon solid oxide fuel cells

Direct carbon solid oxide fuel cells (DC-SOFCs) are recognized as an efficient energy conversion device. With regard to their operation mechanism, the reverse Boudouard reaction rate is the crucial factor influencing cell performance. In this work, a new-type catalyst derived from industrial barium slag (BS) was first developed to enhance the reverse Boudouard reaction and DC-SOFC performance. The chemical composition and micro-morphologies of BS and barium slag-derived catalyst (BSC) were characterized in detail. The superiorities of BS and BSC were reflected in the enhanced DC-SOFC performance and high fuel utilization. The single cell fueled by BSC-loaded carbon yielded the best output of 249 mW cm⁻² at 850 °C. This result was comparable to the 266 mW cm⁻² output of a hydrogen-fueled SOFC due to the superior catalytic activity of metallic catalysts toward carbon gasification. The advantage of the BSC was also observed in the durable operation of the corresponding DC-SOFCs, which lasted for 36.2 h at 50 mA with the fuel utilization of 29.0%. This work provides a new channel for green and efficient utilization of BS and other industrial residues, and a novel option to the development of energy conversion technology.     

Direct liquid-feed fuel cells: Thermodynamic and environmental concerns

The present paper briefly reviews the different direct liquid-feed fuel cells that have been regarded through the open literature. It especially focuses on thermodynamic-energetic data and toxicological–ecological hazards of the chemicals used as liquid fuels. The analysis of those two databases shows that borohydride, ethanol and 2-propanol would be the most adequate liquid fuels for the polymer electrolyte membrane fuel cell-type systems, even if they are inferior to hydrogen. All the fuels and also all the by-products stem from their decomposition are more or less harmful towards health and environment. More particularly, hydrazine should be avoided because it and its by-product are very dangerous. It is to note that the present paper does not intend to review and to compare the performances of those fuel cells because of great differences in the efforts devoted to each of them.