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.     

Performance improvement of a direct carbon solid oxide fuel cell via strontium-catalyzed carbon gasification

As a new way of power generation, direct carbon solid oxide fuel cells (DC-SOFCs) exhibit great potential in solution of energy crisis and environmental pollution. According to the working principle, the cell operation is a kinetically controlled process, and the reverse Boudouard reaction is the rate-determining step of the whole system. In this study, a Sr-based catalyst is successfully introduced to accelerate carbon gasification and thus enhance cell performance of DC-SOFCs. The electrochemical performance of DC-SOFCs operated on coconut active charcoal with various Sr loading contents (3 wt%–10 wt%), are studied and compared with that of DC-SOFCs with traditional Fe-catalyzed carbon fuel. Experimental results demonstrate that the best output of 316 mW cm⁻² is achieved from the single cell powered with 5 wt% Sr-loaded coconut active charcoal at 850 °C, higher than those of DC-SOFCs fueled by pure and 5 wt% Fe-loaded active charcoal. The superiority of the Sr-based catalyst is also demonstrated by the operation stability of the corresponding DC-SOFC, which displays a relatively long operation time of 22.68 h at 0.25 A cm⁻² with the fuel utilization of 18.3%. The SEM/EDX results indicate that the Sr-based catalyst exhibits good stability without agglomeration during cell operation at high temperature. In addition, the carbon gasification mechanism catalyzed by Sr-based catalyst is also proposed on the basis of these properties. This study indicates that the designed Sr-loaded coconut active charcoal is expected to be an alternative carbon fuel for DC-SOFCs.     

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.     

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.     

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.     

Performance of solid oxide fuel cell with chemical looping gasification products as fuel

Chemical looping gasification (CLG) can achieve the utilization of solid fuels for syngas production. The CLG system integrated with solid oxide fuel cell (SOFC) is a promising energy conversion way. In this work, an integration system of CLG and SOFC is evaluated via the implementation of a multi-field coupling modelling, where the products from the CLG are directly transported into the SOFC as the fuel and the coke deposition effect on the cell performance is evaluated. The results reveal that SOFC temperature using pure hydrogen as fuel has an increase of around 4 K compared to that with gas mixture as fuel owing to the inhibition of carbon deposition. It is found that the arrangement of anode and cathode in the countercurrent mode can promote the overall uniformity of current density compared to that in the cocurrent flow. Moreover, the impact of operating parameter of the CLG system on the SOFC performance is also examined. The results demonstrate that the increase of fuel reactor (FR) temperature and H₂O/C molar ratio in the CLG system is beneficial to the inhibition of carbon deposition and the enhancement of the SOFC performance.     

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).     

A performance study of hybrid direct carbon fuel cells: Impact of anode microstructure

Direct carbon fuel cells (DCFCs) have recently attracted great interest because they could provide a considerably more efficient means of power generation in comparison with conventional coal-fired power plants. Among various types of DCFCs under development, a hybrid system offers the combined advantages of solid oxide and molten carbonate electrolytes; however, there is a significant technical challenge in terms of power capability. Here, we report an experimental study demonstrating how anode microstructure influences the power-generating characteristics of hybrid DCFCs. The anode microstructure (pore volume and surface area) is modified by using poly(methyl methacrylate) (PMMA) pore-formers. Polarization studies indicate that cell performance is strongly dependent on the anode surface area rather than on the pore volume. The incorporation of PMMA-derived pores into the anode leads to improved power capability at typical operating temperatures, which is attributed to an enlarged active zone for electrochemical CO oxidation.     

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.     

A novel catalytic layer material for direct dry methane solid oxide fuel cell

The perovskite structured oxide La_0.75Sr_0.25Cr_0.5−xFe_xMn_0.5O_3−δ (LSCFMx, x = 0.05, 0.1, 0.15, 0.2, 0.25) powder is prepared by the liquid phase method, using iron as dopant to replace the chromium. According to XRD patterns, perovskite-like LSCFMx are stable in pure H₂, except for LSCFM0.25. Thus the maximum content of Fe doping is 0.2. The calculated lattice volume increases along with the content of iron and the powders show excellent chemical compatibility with yttria-stabilized zirconia (YSZ). The electrical conductivities for LSCFM0.15 and LSCFM0.2 are very comparative, and they exhibit similar performance as catalytic materials. In contrast, the different sintered temperature with the LSCFM0.2 catalytic layer, at 1300 °C exhibits higher electrochemical performance. When dry methane is used as the fuel, the ohmic resistance and polarization resistance are 0.15 and 0.55 Ω cm², respectively, and the power density reaches 550 mW cm⁻².     

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.     

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.     

Electrochemical oxidation of catalytic grown carbon fiber in a direct carbon fuel cell using Ce0.8Sm0.2O1.9-carbonate electrolyte

The electrochemical oxidation of catalytic grown carbon fiber has been examined in a direct carbon fuel cell (DCFC). The single cell contains a composite electrolyte layer made of a samarium doped ceria (SDC) and a eutectic carbonate phase. The cathode is a mixture of lithiated NiO and the composite electrolyte, while the anode is composed of NiO and SDC powder. Catalytic carbon fiber and the eutectic carbonate is premixed and used as the feed of the anode fuel. The effects of the cell pellet configuration, cathode gas composition and the operation temperature on the DCFC performance have been examined in this work. At 700 °C, the maximum power output achieves 112 mW cm⁻² with a current density of 249 mA cm⁻². The anode off-gas is analyzed with a gas chromatograph, and the Boudouard reaction is found suppressed by the electrical field in the fuel cell operation.     

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.     

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.     

Performance of sorption-enhanced chemical looping gasification system coupled with solid oxide fuel cell using exergy analysis

Coal gasification system integrated with solid oxide fuel cell (SOFC) provides a promising energy conversion way owing to its high efficiency. To get a deep insight into the energy performance of this system, a thermodynamic evaluation is implemented. Meanwhile, the technologies of chemical looping and CO₂ sorption are introduced into this integration system. It is found that the addition of oxygen carrier and sorbent into coal gasification system can promote the output power of the SOFC with a higher exergy destruction, where the exergy efficiency of most modules in the system can reach 80% except tar separation. The results also reveal that a suitable improvement of gasifying agent amount is beneficial to the energy performance of the system. When the H₂O/C molar ratio is increased to 3.0, the SOFC exergy efficiency of 97% can be achieved.     

Performance analysis and parametric study of a solid oxide fuel cell fueled by carbon monoxide

A theoretical model of the solid oxide fuel cell (SOFC) fueled by carbon monoxide is adopted and validated, in which the activation overpotential, concentration overpotential, and ohmic overpotential are regarded as the main sources of voltage losses. Based on the thermodynamic-electrochemical analysis, mathematical expressions of some performance parameters such as the cell potential, power output, efficiency, and entropy production rate are derived. The effects of microstructure parameters such as the electrode porosity, tortuosity, pore size, grain size, etc. on the electrochemical performance characteristics of the SOFC are revealed. Moreover, the effects of some operation conditions such as the current density, anode inlet gas molar fraction, operating temperature, and operating pressure on some important performance parameters of the SOFC are also discussed. It is found that there exist some optimal values of microstructure parameters and operating conditions at which the better performance can be expected. The results obtained in the paper may provide some theoretical guidance for the design and operation of practical SOFCs fueled by coal-derived gases.     

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.     

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.     

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.