Date of Award
Doctor of Philosophy
Materials Science and Engineering
Structure of nickel precipitate from decomposition of urea was found to be alpha-Ni(OH)2. FTIR analysis revealed the intercalation of cyanate (OCN), which is an intermediate product of urea decomposition. This observation implied that the assumption of single step decomposition of urea to carbon dioxide and ammonia was over simplified. Role of critical experimental parameters like initial pH and metal ion concentration on the powder characteristics was carried out. Numerical solutions to reaction pathways predicted significant accumulation of the intermediate cyanate in the time-temperature range investigated. Numerical simulations included the effects of hydrolysis products of Ni2+ and Ni-amine, Ni-cyanate, and Ni-carbonate complexes. Chemical analysis of the precipitate showed a decrease in nitrogen content with increasing reaction times. This was consistent with the predicted decrease in concentration of Ni-cyanate complexes with time.;Layer double hydroxides (LDHs) are intercalation compounds represented by the formula [M2+1-xM3+ x(OH)2]x+[An-x/n ]x-·mH2O. alpha-Ni(OH) 2 and Ni-Al layer double hydroxides precipitated by urea were investigated with FTIR and XPS. The role of cyanate in nucleation and growth of precipitates is demonstrated. In the early stages, cyanate ion is found mainly to be grafted into alpha-Ni(OH)2 via nitrogen, whereas later in the growth stages, it is bonded through oxygen. In LDHs cyanate remains N-bonded. Precipitation with substituted ureas, revealed the link between spectral features and structures observed in XRD patterns. With slower decomposition rates and low levels of supersaturation an extensively hydrated structure was observed. From the two phases of Ni(OH)2, alpha-phase, with its larger interlayer spacing, offers enhanced electrochemical properties but it transforms into thermodynamically stable beta-phase. Stabilizing effects of Ni2+ substitution with Co2+ and Al3+ was investigated. A number of three-component LDHs (TCLDHs) with Ni2+1-(x+y) /Co2+x and Al3+y (x and y were varied between 0.00 and, 0.25) were produced by urea precipitation. From the compositions studied, the ones containing [Al3+] o ≥ 0.015 M resulted with the LDH structure and proved to be stable in the electrolyte for prolonged times. Chronopotentiometry results indicated that TC-LDHs could deliver capacities up to about 30% higher than the beta-phase.
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Mavis, Bora, "Homogeneous precipitation of nickel hydroxide powders " (2003). Retrospective Theses and Dissertations. 731.