Carbon-tolerant anodes

There are a number of informative reviews on anodes for SOFCs [1-5], providing details on processing, fabrication, characterization, and electrochemical behavior of anode materials, especially the nickel-yttria stabilized zirconia (Ni-YSZ) cermet anodes. There are also several reviews dedicated to specific topics such as oxide anode materials [6], carbon-tolerant anode materials [7-9], sulfur-tolerant anode materials [10], and the redox cycling behavior of Ni-YSZ cermet anodes [11], In this chapter, we do not attempt to offer a comprehensive survey of the literature on SOFC anode research instead, we focus primarily on some critical issues in the preparation and testing of SOFC anodes, including the processing-property relationships that are well accepted in the SOFC community as well as some apparently contradictory observations reported in the literature. We will also briefly review some recent advancement in the development of alternative anode materials for improved tolerance to sulfur poisoning and carbon deposition. 

In recent years, there have been numerous studies on alternate anode materials. The areas of interest include carbon-tolerant anode materials, sulfur-tolerant anode materials, and redox-stable anode materials. The idea is that by developing alternative anode materials and structure, the reforming and the desulfurization unit could be eliminated, which would reduce the system complexity and cost dramatically. In this section, the studies into these new, alternative anode materials will be briefly touched upon. Because the number of candidate materials studied is quite large, the amount of study on any individual candidate anode material is rather small, and not much work has been done to reproduce the results reported. Therefore, it is not possible to fully evaluate the real potentials of those new materials proposed by different groups of researchers. Therefore, the focus would be on the fundamental issues for these alternative materials, instead of on the processing and properties of a specific candidate material. 

As stated, one of the fundamental problems encountered in the direct oxidation of hydrocarbon fuels in SOFCs is carbon deposition on the anode, which quickly deactivates the anode and degrades cell performance. The possible buildup of carbon can lead to failure of the fuel-cell operation. Applying excess steam or oxidant reagents to regenerate anode materials would incur significant cost to SOFC operation. The development of carbon tolerant anode materials was summarized very well in several previous reviews and are not repeated here [7-9], In this section, the focus will be on theoretical studies directed toward understanding the carbon deposition processes in the gas-surface interfacial reactions, which is critical to the... 

As discussed earlier, the presence of tar among the products of gasification reduces gas yield and conversion efficiency. In addition, these contaminants are responsible for carbon deposition that can block the porous media of a fuel cell anode. The tolerance limit of... 

This failure mechanism can have significant impact on the ability of the anode to tolerate adsorbed contaminants. Similar to the impact of carbon corrosion on the cathode, the reduced electrochemically active catalyst surface area becomes very sensitive to the presence of contaminants. This is very important, for example, for operation on reformate where even small amounts of carbon monoxide can result in significant performance loss. 

As with the platinum anode catalyst in the PEM fuel cell, the anode of the PAFC may be poisoned by carbon monoxide in the fuel gas. The CO occupies catalyst sites. Such CO is produced by steam reforming and for the PAFC the level that the anode can tolerate is dependent on the temperature of the cell. The higher the temperature, the greater is the tolerance for CO. The absorption of CO on the anode electrocatalyst is reversible and CO will be desorbed if the temperature is raised. Any CO has some effect on the PAFC performance, but the effect is not nearly so important as in Ihe PEMFC. At a working temperature above 190°C, a CO level of up to 1% is acceptable, but some quote a level of 0.5% as the target. The methods used to reduce the CO levels are discussed in the next chapter, especially in Section 8.4.9. 

It is well established that sulfur compounds even in low parts per million concentrations in fuel gas are detrimental to MCFCs. The principal sulfur compound that has an adverse effect on cell performance is H2S. A nickel anode at anodic potentials reacts with H2S to form nickel sulfide. Chemisorption on Ni surfaces occurs, which can block active electrochemical sites. The tolerance of MCFCs to sulfur compounds is strongly dependent on temperature, pressure, gas composition, cell components, and system operation (i.e., recycle, venting, and gas cleanup). Nickel anode at anodic potentials reacts with H2S to form nickel sulfide. Moreover, oxidation of H2S in a combustion reaction, when recycling system is used, causes subsequent reaction with carbonate ions in the electrolyte [1]. Some researchers have tried to overcome this problem with additional device such as sulfur removal reactor. If the anode itself has a high tolerance to sulfur, the additional device is not required, hence, cutting the capital cost for MCFC plant. To enhance the anode performance on sulfur tolerance, ceria coating on anode is proposed. The main reason is that ceria can react with H2S [2,3] to protect Ni anode. 

Poisoning of platinum fuel cell catalysts by CO is undoubtedly one of the most severe problems in fuel cell anode catalysis. As shown in Fig. 6.1, CO is a strongly bonded intermediate in methanol (and ethanol) oxidation. It is also a side product in the reformation of hydrocarbons to hydrogen and carbon dioxide, and as such blocks platinum sites for hydrogen oxidation. Not surprisingly, CO electrooxidation is one of the most intensively smdied electrocatalytic reactions, and there is a continued search for CO-tolerant anode materials that are able to either bind CO weakly but still oxidize hydrogen, or that oxidize CO at significantly reduced overpotential. 

However, the Pt anode is seriously poisoned by trace amounts of carbon monoxide in reformates (fuel gas reformed from hydrocarbon), because CO molecules strongly adsorb on the active sites and block the HOR [Lemons, 1990 Igarashi et ah, 1993]. Therefore, extensive efforts have been made to develop CO-tolerant anode catalysts and cell operating strategies to suppress CO poisoning, such as anode air-bleeding or pulsed discharging. 

Carbon Monoxide. Carbon monoxide, a fuel in high-temperature cells (MCFC and SOFC), is preferentially absorbed on noble metal catalysts that are used in low-temperature cells (PAFC and PEFC) in proportion to the hydrogen-to-CO partial pressure ratio. A particular level of carbon monoxide yields a stable performance loss. The coverage percentage is a function of temperature, and that is the sole difference between PEFC and PAFC. PEFC cell limits are < 50 ppm into the anode major U.S. PAFC manufacturers set tolerant limits as < 1.0% into the anode MCFC cell limits for CO and H20 shift to H2 and C02 in the cell as the H2 is consumed by the cell reaction due to a favorable temperature level and catalyst. 

The development of new, alternative anode materials has recently attracted considerable interest. Several new materials show improved tolerance to sulfur poisoning and carbon deposition. However, critical issues associated with each candidate material are yet to be overcome. The traditional Ni-YSZ cermet anode still offers the best performance when clean hydrogen is used as the fuel and will continue to play an important role in SOFCs. 

Alloying the nickel of the anode to improve tolerance for fuel contaminants has been explored. Gold and copper alloying decreases the catalytic activity for carbon deposition, while dispersing the anode with a heavy transition metal catalyst like tungsten improves sulfur resistance. Furthermore, ceria cermets seem to have a higher sulfur tolerance than Ni-YSZ cermets [75],... 

The MCFC has some disadvantages, however the electrolyte is very corrosive and mobile, and a source of CO2 is required at the cathode (usually recycled from anode exhaust) to form the carbonate ion. Sulfur tolerance is controlled by the reforming catalyst and is low, which is the same for the reforming catalyst in all cells. Operation requires use of stainless steel as the cell hardware material. The higher temperatures promote material problems, particularly mechanical stability that impacts life. 

Solid Particulates These contaminants can originate from a variety of sources, and their presence is a major concern because they can block gas passages and/or the anode surface. Carbon deposition and conditions that can be used to control its formation have been discussed earlier in this section. Solid particles such as ZnO, which is used for sulfur removal, can be entrained in the fuel gas leaving the desulfurizer. The results by Pigeaud (72) indicate that the tolerance limit of MCFCs to particulates larger than 3 pm diameter is <0.1 g/1. 

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