Development of tubular hybrid direct carbon fuel cell

The hybrid direct carbon fuel cell is a direct carbon fuel cell concept that combines a solid oxide fuel cell with a molten carbonate fuel cell electrode. This offers efficient conversion of coal or biomass derived carbons to electricity. In this study we aim to improve the electrical performance of this cell by using gadolinia doped ceria (GDC) as either a protection layer over a YSZ electrolyte or as the electrolyte itself. In our study, the electrical performance of several tubular cell geometries were investigated using impedance spectroscopy both with and without gas flows of carbon dioxide or nitrogen. Integrity of microstructure including possible layer delamination effects were investigated by SEM. Promising values of power and resistance were observed using a GDC material as electrolyte at intermediate temperature reducing the operation temperature compared to YSZ, doubling the power of each cell.     

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.     

Investigation of direct carbon conversion at the surface of a YSZ electrolyte in a SOFC

Fuel cells offer a promising way to produce electricity efficiently. In this work, a direct carbon fuel cell (DCFC) based on a solid oxide fuel cell (SOFC) has been investigated, in which solid carbon has been used as fuel in form of a pellet. The DCFC is an interesting technology because it offers the possibility to use, as fuel source, available and abundant raw materials with only minor pretreatment. Moreover, the thermodynamic efficiency slightly exceeds 100% in a wide temperature range due to the positive near-zero value of reaction entropy change. As pure carbon dioxide is produced at the anode, it can be easily captured and sequestered. Direct carbon conversion is competed by the Boudouard reaction, which produces carbon monoxide at high operating temperatures. This reaction is endothermic and leads to a fuel loss. The present paper relates to the contribution of both reactions by a long-term run over about 12 h with a non-porous anode layer.     

直接碳燃料电池性能研究

直接碳燃料电池(DCFC)勿需碳和氧气气化、重整,而直接通过电化学反应产生电能,效率可达80%,燃料的理论利用率可达100%,是一种高效、清洁的燃料电池.文章所介绍的组装DCFC单体电池,以石墨作阳极,不锈钢作阴极,加湿氧气作氧化剂,采用熔融氢氧化物作电解质,并掺入一定量的催化剂,该电池工作温度为500～700℃.对不同工作温度、不同电解质和不同氧气流量下DCFC的输出性能进行了试验研究.结果表明:随着工作温度的升高,电池输出性能有很大提高;KOH比NaOH的导电性好,电池运行更稳定,更有利于电池的输出;氧气流量为70mL/min,温度为650℃时,该电池的输出性能最佳,最大电流密度、功率密度分别为118mA/cm2和0.054 W/cm2,开路电压达到0.76 V.     

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.     

Mixed ionic electronic conducting perovskite anode for direct carbon fuel cells

The conversion of carbonaceous materials to electricity in a Direct Carbon Fuel Cell (DCFC) offers the most efficient process with theoretical electric efficiency close to 100%. One of the key issues for fuel cells is the continuous availability of the fuel at the triple phase boundaries between fuel, electrode and electrolyte. While this can be easily achieved with the use of a porous fuel electrode (anode) in the case of gaseous fuels, there are serious challenges for the delivery of solid fuels to the triple junctions. In this paper, a novel concept of using mixed ionic electronic conductors (MIEC) as anode materials for DCFCs has been discussed. The lanthanum strontium cobalt ferrite, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ (LSCF) was chosen as the first generation anode material due to its well known high mixed ionic and electronic conductivities in air. This material has been investigated in detail with respect to its conductivity, phase and microstructural stability in DCFC operating environments. When used both as the anode and cathode in a DCFC, power densities in excess of 50 mW/cm² were obtained at 804 °C in electrolyte supported small button cells with solid carbon as the fuel. The concept of using the same anode and cathode material has also been evaluated in electrolyte supported thick wall tubular cells where power densities around 25 mW/cm² were obtained with carbon fuel at 820 °C in the presence of helium as the purging gas. The concept of using a mixed ionic electronic conducting anode for a solid fuel, to extend the reaction zone for carbon oxidation from anode/electrolyte interface to anode/solid fuel interface, has been demonstrated.     

Performance of direct carbon fuel cell

A direct carbon fuel cell (DCFC) is a variation of the molten carbonate fuel cell (MCFC) which converts the chemical energy of carbon directly into electrical energy. Thus, the energy conversion efficiency is very high and correspondingly CO₂ emission is very low for given power output. DCFC as a high temperature fuel cell performs better at elevated temperatures (>800 °C) but because of the corrosive nature of the molten carbonates at elevated temperatures the degradation of cell components becomes an issue when DCFC is operated for an extended period of time.We explored the DCFC performance at lower temperatures (at 700 °C and less) using different sources of carbon, different compositions of electrolytes and some additives on the cathode surface to increase catalytic activity. Experiments showed that with petroleum coke as a fuel at low temperatures the ternary eutectic (43.4 mol % Li₂CO₃ - 31.2 mol% Na₂CO₃ - 25.4 mol % K₂CO₃) spiked by 20 wt % Cs₂CO₃ performed better than any binary or ternary eutectics described in the published work by other researchers. Maximum power output achieved at 700 °C was 49 mW/cm² at a current density of 78 mA/cm² when modified cathode was fed with O₂/CO₂ gases.     

A direct methanol fuel cell system to power a humanoid robot

In this study, a direct methanol fuel cell (DMFC) system, which is the first of its kind, has been developed to power a humanoid robot. The DMFC system consists of a stack, a balance of plant (BOP), a power management unit (PMU), and a back-up battery. The stack has 42 unit cells and is able to produce about 400 W at 19.3 V. The robot is 125 cm tall, weighs 56 kg, and consumes 210 W during normal operation. The robot is integrated with the DMFC system that powers the robot in a stable manner for more than 2 h. The power consumption by the robot during various motions is studied, and load sharing between the fuel cell and the back-up battery is also observed. The loss of methanol feed due to crossover and evaporation amounts to 32.0% and the efficiency of the DMFC system in terms of net electric power is 22.0%.     

Enhancing triple-phase boundary at fuel electrode of direct carbon fuel cell using a fuel-filled ceria-coated porous anode

A new type of high-temperature fuel cell using solid carbon as a fuel, which is called a direct carbon fuel cell (DCFC), recently attracts scientific and industrial attention due to its excellent electrochemical efficiency, less production of CO₂, and no need of CO₂ separation. However, the state-of-the-art technology on the DCFC still stays in an idea developing stage, mainly because of fuel-related difficulties: a discontinuous fuel supply and a very limited formation of triple phase boundary. In this study, we focused on how to enhance the formation of triple phase boundary at the fuel electrode: using a porous Ni anode filled with carbon particles to enhance the fuel-electrode physical contact and making the porous anode wettable by ceria coating the anode. We demonstrated for the first time that the two ideas are quite successful, leading to 700% increase in a maximal power density and 500% increase in a maximal current density with respect to the standard case.     

A three-dimensional two-phase flow model for a liquid-fed direct methanol fuel cell

A three-dimensional, two-phase, multi-component model has been developed for a liquid-fed DMFC. The modeling domain consists of the membrane, two catalyst layers, two diffusion layers, and two channels. Both liquid and gas phases are considered in the entire anode, including the channel, the diffusion layer and the catalyst layer; while at the cathode, two phases are considered in the gas diffusion layer and the catalyst layer but only single gas phase is considered in the channels. For electrochemical kinetics, the Tafel equation incorporating the effects of two phases is used at both the cathode and anode sides. At the anode side the presence of gas phase reduces the active catalyst areas, while at the cathode side the presence of liquid water reduces the active catalyst areas. The mixed potential effects due to methanol crossover are also included in the model. The results from the two-phase flow mode fit the experimental results better than those from the single-phase model. The modeling results show that the single-phase models over-predict methanol crossover. The modeling results also show that the porosity of the anode diffusion layer plays an important role in the DMFC performance. With low diffusion layer porosity, the produced carbon dioxide cannot be removed effectively from the catalyst layer, thus reducing the active catalyst area as well as blocking methanol from reaching the reaction zone. A similar effect exits in the cathode for the liquid water.     

A comprehensive review of direct carbon fuel cell technology

Fuel cells are under development for a range of applications for transport, stationary and portable power appliances. Fuel cell technology has advanced to the stage where commercial field trials for both transport and stationary applications are in progress. The electric efficiency typically varies between 40 and 60% for gaseous or liquid fuels. About 30–40% of the energy of the fuel is available as heat, the quality of which varies based on the operating temperature of the fuel cell. The utilisation of this heat component to further boost system efficiency is dictated by the application and end-use requirements. Fuel cells utilise either a gaseous or liquid fuel with most using hydrogen or synthetic gas produced by a variety of different means (reforming of natural gas or liquefied petroleum gas, reforming of liquid fuels such as diesel and kerosene, coal or biomass gasification, or hydrogen produced via water splitting/electrolysis). Direct Carbon Fuel Cells (DCFC) utilise solid carbon as the fuel and have historically attracted less investment than other types of gas or liquid fed fuel cells. However, volatility in gas and oil commodity prices and the increasing concern about the environmental impact of burning heavy fossil fuels for power generation has led to DCFCs gaining more attention within the global research community. A DCFC converts the chemical energy in solid carbon directly into electricity through its direct electrochemical oxidation. The fuel utilisation can be almost 100% as the fuel feed and product gases are distinct phases and thus can be easily separated. This is not the case with other fuel cell types for which the fuel utilisation within the cell is typically limited to below 85%. The theoretical efficiency is also high, around 100%. The combination of these two factors, lead to the projected electric efficiency of DCFC approaching 80% - approximately twice the efficiency of current generation coal fired power plants, thus leading to a 50% reduction in greenhouse gas emissions. The amount of CO₂ for storage/sequestration is also halved. Moreover, the exit gas is an almost pure CO₂ stream, requiring little or no gas separation before compression for sequestration. Therefore, the energy and cost penalties to capture the CO₂ will also be significantly less than for other technologies. Furthermore, a variety of abundant fuels such as coal, coke, tar, biomass and organic waste can be used. Despite these advantages, the technology is at an early stage of development requiring solutions to many complex challenges related to materials degradation, fuel delivery, reaction kinetics, stack fabrication and system design, before it can be considered for commercialisation. This paper, following a brief introduction to other fuel cells, reviews in detail the current status of the direct carbon fuel cell technology, recent progress, technical challenges and discusses the future of the technology.     

Scaling up of the hybrid direct carbon fuel cell technology

A hybrid direct carbon fuel cell (HDCFC), combining molten carbonate fuel cell (MCFC) and solid oxide fuel cell (SOFC) technologies, is capable of converting solid carbon directly into electrical energy without intermediate reforming. The performance level achieved on small-scale cells (area <4 cm²) suggests that engineering developments should now be undertaken to scale up and demonstrate the feasibility of practical systems. The scaling up of the HDCFC through the design and test of single stack repeat unit with realistic cell sizes was investigated in this study. A single cell of ∼12.56 cm² active area produced a maximum power of ∼1.2 W at 800 °C and a current density of ∼200 mA cm² at 0.6 V, using wood-based pyrolyzed medium density fiberboard (p-MDF) as fuel. In comparison, the HDCFC with activated carbon as fuel produced a maximum power density of 36 and 53 mW cm⁻² at 700 and 800 °C, respectively, and an electric efficiency of ∼40% evaluated under 0.7 V for 17 h at 700 °C. These results demonstrated the applicability of HDCFC to practical systems while stack units were operated in batch mode and an appropriate fuel feeding mechanism has to be designed. Moreover, more engineering advances should be done to enhance power output since a HDCFC stack unit involves multiple challenges that have not been addressed yet, including system configuration and corrosion protection, and durability.     

A novel direct ethanol fuel cell with high power density

A new type of direct ethanol fuel cell (DEFC) that is composed of an alkaline anode and an acid cathode separated with a charger conducting membrane is developed. Theoretically it is shown that the voltage of this novel fuel cell is 2.52 V, while, experimentally it has been demonstrated that this fuel cell can yield an open-circuit voltage (OCV) of 1.60 V and a peak power density of 240 mW cm⁻² at 60 °C, which represent the highest performance of DEFCs that has so far been reported in the open literature.     

Feedforward-feedback control of a solid oxide fuel cell power system

One of the main challenges for wide-spread utilization of the solid oxide fuel cell (SOFC) power systems is how to achieve high electrical efficiency without increasing the degradation rate of the fuel cells. To run the SOFC power system at high efficiency over a long period of time, properly designed controllers are indispensable.Although a number of various approaches to control SOFC have been proposed so far, it seems that the design of control system, along with simple tuning procedure, has not been treated in a consistent manner. This issue is addressed in the present paper resulting in a feedforward-feedback control structure. The feedforward part is based on the stoichiometry of electro-oxidation, reforming and combustion reactions, which allow immediate response to variable current demand. The feedback part performs additional fine adjustment of fuel and air supply in order to minimize the undesired system temperatures variations. The selection of pairings of manipulated and controlled variables for control is based on physical knowledge of the system. Input/output pairing for single-loop feedback control is assessed by the relative gain analysis. An efficient procedure for tuning the parameters of the feedback controllers is suggested, relying on simple open-loop step responses of the system.The proposed low-level control is assessed on a detailed physical model of a 2.5 kW SOFC power system by simulating two nonstationary load regimes. Simulations show that the control provides a robust operation under large load variations while meeting the operating constraints. Due to its simplicity, the control is feasible for implementation on a real SOFC system.     

Online analysis of carbon dioxide from a direct ethanol fuel cell

Carbon dioxide yields from a direct ethanol fuel cell have been monitored by using a commercial infrared CO₂ monitor. The time dependence is reported as a function of temperature, current density, and anode catalyst (Pt vs. PtRu). Yields increased strongly with temperature, with a Faradaic yield of 76% being obtained at 100 °C with a Pt black anode. PtRu gave lower yields than Pt by a factor of ca. 3 at 80 and 100 °C, but higher yields than Pt at ambient temperature. The superior ability of PtRu to strip adsorbed CO is important at low temperatures, but not a key factor at 100 °C.     

High power direct methanol fuel cell for mobility and portable applications

Here, we report on a low cost and novel architecture Direct Methanol Fuel Cell (DMFC) for mobility and portable applications. DMFC is fast charged by a low cost liquid fuel, thus it is expected to be competitive with the hydrogen gas fuel cells. Our research efforts have culminated in the outstanding performance of DMFC with very high power density of 181 mW cm⁻² at 80 °C, under very low air pressure of 0.05atm. This exceptional DMFC performance was achieved by a modification of the hydrophobicity of the BPP (Bi-Polar Plate) flow field channels. Our study of the effects of the hydrophobicity of bipolar flow field plates give rise to fundamental understanding of the relationship between the two-phase flow, that occurs in the flow channels of the bipolar plates of DMFC cells. To the best of our knowledge, such performance was never achieved prior to this work.     

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).     

Two-phase hydrodynamics in a miniature direct methanol fuel cell

We present controlled experiments on a miniature direct methanol fuel cell (DMFC) to study the effects of methanol flow rate, current density, and void fraction on pressure drop across the DMFC anode. We also present an experimental technique to measure void fraction, liquid slug length, and velocity of the two-phase slug flow exiting the DMFC. For our channel geometry in which the diameter of the largest inscribed sphere (a) is 500 μm, pressure drop scales with the number of gas slugs in the channel, surface tension, and a. This scaling demonstrates the importance of capillary forces in determining the hydrodynamic characteristics of the DMFC anode. This work is aimed at aiding the design of fuel pumps and anode flow channels for miniature DMFC systems.     

A novel anti islanding detection method for grid connected fuel cell power generation systems

Renewable energy sources have been developed rapidly all around the world, and one of these green energy sources is hydrogen energy. The fuel cell systems have become prominent in renewable energy sources because of its minimal dimensions and energy conversion method. There have been developed, some applications, especially in domestic and automotive areas, and fuel cell systems are also have been started to use in grid connected systems. Fuel cell systems must have some electrical connection standards while they connected to an electrical grid. One of these electrical conditions and may be the most important one is unplanned islanding condition. Islanding is a very dangerous situation because it can damage to the fuel cell and related electrical systems and also working people have been at risk in islanding situation on the grid. In this study, a novel islanding detection method was introduced for grid connected fuel cell systems. 0.5 kW solid oxide fuel cell (SOFC) system used in developed experimental system and a novel anti islanding detection method was researched by using an effective method. The proposed method was also developed by using Matlab Simulink and its useful tools. The developed islanding detection method is robust, reliable and has a fast response time, according to present methods. The results confirm the suggested conditions, and it can be seen in this method, it can also be adapted easily to the grid connected fuel cell systems.     

An ultrasound enhanced direct methanol fuel cell

A novel direct methanol fuel cell (DMFC) incorporating an ultrasonic transducer is introduced based on a recent provisional patent application [J. Ge, J. Han, H. Liu, Ultrasounically enhanced fuel cell system, U.S. Provisional Patent Application No. 60/815,268, June 21, 2006]. The ultrasound transducer is embedded in the methanol supply line and is used to enhance the performance of a DMFC. The technique of introducing ultrasound through methanol supply line significantly reduced the potential losses in ultrasound transmission to the reaction sites of the fuel cell. Series of experiments have been conducted to study the effect of the ultrasound on the performance of the DMFC. The experimental results showed that the high-frequency vibrations of the ultrasound through the methanol supply line enhance the cell performance significantly and consistently. The experimental results unequivocally demonstrated the feasibility of using ultrasound to enhance DMFC performance and the effectiveness of introducing ultrasound into a DMFC via methanol supply line to minimize the wave transmission losses.