Anode Interactions with Coal Gas Contaminants

This report describes efforts to characterize the interactions nickel anodes with phosphorus in coal gas using three different button cell configurations to emphasize particular degradation modes. Important parameters addressed included contaminant concentration, temperature, reaction time, fuel utilization, and current density. In addition, coupon tests in flow-through and flow-by arrangements were conducted to complement cell tests. The studies have involved extensive electrochemical testing using both dc and ac methods. Post-test analyses to determine the composition and extent of nickel modification are particularly important to understanding reactions that have occurred. This report also provides a thermodynamic assessment of contaminant reactions with nickel in a coal gas environment with regard to alteration phase formation. Contaminants addressed were phosphorus, arsenic, sulfur, selenium, and antimony. Phosphorus was found to interact strongly with nickel and result in extensive alteration phase formation, consistent with expectations based on thermodynamic properties. Even in button cell tests where the fuel utilization was low, phosphorus was found to be nearly completely captured by the nickel anode. For anode-supported cells, an important degradation mode involved loss of electronic percolation, the result of nickel phosphide formation, grain growth, and inducement of micro-fractures within the anode support. Even with excessive anode support conversion, electrochemical degradation rates were often very low. This is attributed to a “shadowing effect,” whereby a dense structure such as current leads prevent phosphorus from reacting with the nickel directly underneath. This effect maintains an electrical pathway to the active interface, and allows the cell to operate with minimal degradation until the anode is essentially completely consumed. In a planar stack, ribs on the interconnect plate would be expected to provide this conductive pathway in the event of phosphorus exposure. When phosphorus interactions proceeded to the active interface, most easily observed in tests with electrolyte-supported cells having a thin anode, the electrochemical performance decreased considerably