Effect of Gaseous Impurities on Long-Term Thermal Cycling and Aging Properties of Complex Hydrides for Hydrogen Storage

[摘要] This program was dedicated to understanding the effect of impurities on Long-Term Thermal Cycling and aging properties of Complex Hydrides for Hydrogen Storage. At the start of the program we found reversibility between Li2NH+LiH LiH+LiNH2 (yielding ~5.8 wt.%H capacity). Then we tested the effect of impurity in H2 gas by pressure cycling at 255?��C; first with industrial gas containing ppm levels of O2 and H2O as major impurities. Both these impurities had a significant impact on the reversibility and decreased the capacity by 2.65 wt.%H. Further increase in number of cycles from 500 to 1100 showed only a 0.2 wt%H more weight loss, showing some capacity is still maintained after a significant number of cycles. The loss of capacity is attributed to the formation of ~55 wt% LiH and ~30% Li2O, as major contaminant phases, along with the hydride Li2NH phase; suggesting loss of nitrogen during cycling. The effect of 100 ppm H2O in H2 also showed a decrease of ~2.5 wt.%H (after 560 cycles), and 100ppm O2 in H2; a loss of ~4.1 wt.%. Methane impurity (100 ppm, 100cycles), showed a very small capacity loss of 0.9 wt.%H under similar conditions. However, when Li3N was pressure cycled with 100ppmN2-H2 there were beneficial effects were observed (255oC); the reversible capacity increased to 8.4wt.%H after 853 cycles. Furthermore, with 20 mol.%N2-H2 capacity increased to ~10 wt.%H after 516 cycles. We attribute this enhancement to the reaction of nitrogen with liquid lithium during cycling as the Gibbs free energy of formation of Li3N (Go = -98.7 kJ/mol) is more negative than that of LiH (Go = -50.3 kJ/mol). We propose that the mitigation of hydrogen capacity losses is due to the destabilization of the LiH phase that tends to accumulate during cycling. Also more Li2NH phase was found in the cycled product. Mixed Alanates (3LiNH2:Li3AlH6) showed that 7 wt% hydrogen desorbed under dynamic vacuum. Equilibrium experiments (maximum 12 bar H2) showed up to 4wt% hydrogen reversibly stored in the material after the first desorption. The activation energy was found to be 51 kJ/mol, as compared to 81 kJ/mol for pure lithium alanate. It is proposed that based on the data obtained and CALPHAD modeling that the improvement in cycling is due to the formation of pure lithium (liquid at 255?��C), which is able to react with nitrogen specifically forming Li3N. The presence of nitrogen in the 80/20 molar mixtures in a hydride bed along with hydrogen causes Li to form Li3N rather than LiH, and subsequently regenerates the Li2NH phase and yields a ~10 wt.%H reversibly.

[发布日期] 2011-03-28

[学科分类] 再生能源与代替技术

[关键词] ACTIVATION ENERGY;AGING;CAPACITY;DESORPTION;FREE ENTHALPY;HYDRIDES;HYDROGEN;HYDROGEN STORAGE;IMPURITIES;LITHIUM;METHANE;MITIGATION;MIXTURES;NITROGEN;THERMAL CYCLING Complex metal Hydrides;Hydrogen storage;Li3N-H;H2-N2 gas mixtures;Phase diagrams of Li-N-H;reversible Imide-amide