Anode material development

Jiang SP and Chan SH. A review on anode materials development in solid oxide fuel cells. J Mater Sci 2004 39 4405 1439. 

Marina O and Stevenson J. SOFC Anode Materials Development at PNNL. In 2004 Office of Fossil Energy Fuel Cell Program Annual Report, Office of Fossil Energy, U.S. Department of Energy, 2004 90-92. 

Cells operating at low (2,80,81) and high (79,82) temperatures were developed first, but discontinued because of corrosion and other problems. The first medium temperature cell had an electrolyte composition corresponding to KF 3HF, and operated at 65—75°C using a copper cathode and nickel anodes. A later cell operated at 75°C and used KF 2.2HF or KF 2HF as electrolyte (83,84), and nickel and graphite as anode materials. 

Cathodic protection of reinforcing steel with impressed current is a relatively new protection method. It was used experimentally at the end of the 1950s [21,22] for renovating steel-reinforced concrete structures damaged by corrosion, but not pursued further because of a lack of suitable anode materials so that driving voltages of 15 to 200 V had to be applied. Also, from previous experience [23-26], loss of adhesion between the steel and concrete due to cathodic alkalinity [see Eqs. (2-17) and (2-19)] was feared, which discouraged further technical development. 

Table 10.9 lists some common zinc anode alloys. In three cases aluminium is added to improve the uniformity of dissolution and thereby reduce the risk of mechanical detachment of undissolved anode material . Cadmium is added to encourage the formation of a soft corrosion product that readily crumbles and falls away so that it cannot accumulate to hinder dissolution. The Military Specification material was developed to avoid the alloy passivating as a result of the presence of iron . It later became apparent that this material suffered intergranular decohesion at elevated temperatures (>50°C) with the result that the material failed by fragmentation". The material specified by Det Norske Veritas was developed to overcome the problem the aluminium level was reduced under the mistaken impression that it produced the problem. It has since been shown that decohesion is due to a hydrogen embrittlement mechanism and that it can be overcome by the addition of small concentrations of titanium". It is not clear whether... 

The application of sacrificial anodes for the protection of structures requires the development of suitable anode materials for the exposure environment. Screening tests enable the rapid selection of materials which show potential as candidates for the given application. These tests may typically use a single parameter (e.g. operating potential at a defined constant current density) as a pass/fail criterion and are normally of short duration (usually hours) with test specimen weights of the order of hundreds of grams. The tests are not intended to simulate field conditions precisely. 

These are iron alloys that contain 14-18% Si and are reported as first being developed in 1912 , although it was not until 1954 that they were first evaluated for use as impressed-current anode material in cathodic protection. Its major disadvantage is that it is a hard brittle material unable to sustain thermal or mechanical shock. 

The thermodynamic properties of magnesium make it a natural choice for use as an anode material in rechargeable batteries, as it may provide a considerably higher energy density than the commonly used lead-acid and nickel-cadmium systems, while in contrast to Pb and Cd, magnesium is inexpensive, environmentally friendly, and safe to handle. However, the development of Mg-ion batteries has so far been limited by the kinetics of Mg " " diffusion and the lack of suitable electrolytes. Actually, in spite of an expected general similarity between the processes of Li and Mg ion insertion into inorganic host materials, most of the compounds that exhibit fast and reversible Li ion insertion perform very poorly in Mg " ions. Hence, there... 

TLC is used to determine copper in aluminum alloys. The process involves the sampling of the investigated material by anodic dissolution, development of TLC plate with acetone -f HCl -f HjO (70 15 15), and the identification of analyte by 1-(2-pyridylazo)-2-naphthol [70]. A TLC system comprising silica gel as stationary... 

Based on the anode material employed, eight (8) subdivisions (A-H) have been developed by the U.S. EPA.5 As may be noted (Table 32.1), the zinc anode is divided into two groups (subcategories D and G) based on the electrolyte types. This difference is also reflected in the substantial differences in the manufacture, as well as the waste generated by the two groups. Although a subcategory of nuclear batteries is indicated, hardly any data exist that describes its construction, leave alone the waste characteristics. Similar paucity in information exists on thermal batteries (such as calcium batteries), whose production and use are limited to few operations, especially in... 

The Li-Ion system was developed to eliminate problems of lithium metal deposition. On charge, lithium metal electrodes deposit moss-like or dendrite-like metallic lithium on the surface of the metal anode. Once such metallic lithium is deposited, the battery is vulnerable to internal shorting, which may cause dangerous thermal run away. The use of carbonaceous material as the anode active material can completely prevent such dangerous phenomenon. Carbon materials can intercalate lithium into their structure (up to LiCe). The intercalation reaction is very reversible and the intercalated carbons have a potential about 50mV from the lithium metal potential. As a result, no lithium metal is found in the Li-Ion cell. The electrochemical reactions at the surface insert the lithium atoms formed at the electrode surface directly into the carbon anode matrix (Li insertion). There is no lithium metal, only lithium ions in the cell (this is the reason why Li-Ion batteries are named). Therefore, carbonaceous material is the key material for Li-Ion batteries. Carbonaceous anode materials are the key to their ever-increasing capacity. No other proposed anode material has proven to perform as well. The carbon materials have demonstrated lower initial irreversible capacities, higher cycle-ability and faster mobility of Li in the solid phase. 

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... 

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. 

Similarly to the case of direct-oxidation anode materials, sulfur-tolerant anode materials based on sulfides [6, 7] or double-perovskite oxides have special requirements for their processing into SOFC layers. For example, nickel sulfide-promoted molybdenum sulfide is tolerant to high sulfur levels [7], However, it has a low melting temperature [6] that has resulted in the development of cobalt sulfide as a stabilizer of the molybdenum sulfide catalyst [6], CoS-MoS2 admixed with Ag has an even higher performance in H2S-containing fuels than in pure H2 [6]. However, processing methods such as PS, infiltration, or sol-gel techniques that can process... 

Combining the above evidences, Huang et al. further concluded that the improvement in the low-temperature performances of lithium ion cells would eventually rely on the effort to develop anode materials of high lithium diffusion coefficients instead of the electrolytes and SEI that were less resistant. 

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