Phase structure and electrochemical characteristics of Co-free La0.7Ce0.3(Ni3.65Cu0.75Mn0.35Al0.15(Fe0.43B0.57)0.10)x (0.90≤x≤1.10) al-loys were investigated. When x was 0.90, the alloy was composed of LaNi5, La3Ni13B2 and Ce2Ni7 phases. The Ce2Ni7 phase disappeared, and the abundant of La3Ni13B2 phase decreased when x increased to 0.95. When x was 1.00 or higher the alloys consisted of LaNi5 phase. The lat-tice parameter a and the cell volume V of the LaNi5 phase decreased, and the c/a ratio of the LaNi5 phase increased with x value increasing. Maximum discharge capacity of the alloy electrodes first increased and then decreased with x value increasing from 0.90 to 1.10, and the highest value was obtained when x was 1.00. High-rate dischargeability at the discharge current density of 1200 mA/g increased from 50.7% (x= 0.90) to 64.1% (x=1.10). Both the charge-transfer reaction at the electrode/electrolyte interface and the hydrogen diffusion in the alloy were responsible for the high-rate dischargeability. Cycling capacity retention rate at 100th cycle (S100) gradually increased from 77.3% (x= 0.90) to 84.6% (x=1.10), which resulted from the increase in Ni content and the c/a ratio of the LaNi5 phase with x value increasing.
The phase structure and hydrogen storage properties of LaMg 3.70 Ni 1.18 alloy were investigated. The LaMg 3.70 Ni 1.18 alloy consists of main LaMg 2 Ni phase, minor La 2 Mg 17 and LaMg 3 phases. The alloy can be activated in the first hydriding/dehydriding process, and initial LaMg 2 Ni, La 2 Mg 17 , and LaMg 3 phases transfer to LaH 2.34 , Mg, and Mg 2 Ni phases after activation. The reversible hydrogen storage capacity of the LaMg 3.70 Ni 1.18 alloy is 2.47 wt.% at 558 K, which is higher than that of the LaMg 2 Ni alloy. The pressure-composition-temperature (PCT) curves display two hydriding plateaus, corresponding to the formation of MgH 2 and Mg 2 NiH 4 . However, only one dehydriding plateau is observed, owing to the synergetic effect of hydrogen desorption between MgH 2 and Mg 2 NiH 4 . The uptake time for hydrogen content to reach 99% of saturated state is less than 250 s, and 90% hydrogen can be released in 1200 s in the experimental conditions, showing fast kinetics in hydriding and dehydriding. The activation energies of the LaMg 3.70 Ni 1.18 alloy are -51.5 ± 1.1 kJ/mol and -57.0 ± 0.6 kJ/mol for hydriding and dehydriding, respectively. The hydriding/dehydriding kinetics of the LaMg 3.70 Ni 1.18 alloy is better than that of the Mg 2 Ni alloy, owing to the lower activation energy values.
LI JinhuaLIU BaozhongHAN ShuminHU LinZHAO XinWANG Mingzhi
Microstructure and electrochemical characteristics of La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-x(V0.81Fe0.19)x hydrogen storage alloys were investigated. XRD indicated that La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-x(V0.81Fe0.19)x alloys consisted of a single phase with CaCu5-type structure, and the lattice parameter a and cell volume V increased with increasing x value. The maximum discharge capacity first increased from 319.0 (x=0) to 324.0 mAh/g (x=0.05), and then decreased to 307.0 mAh/g (x=0.20). The high-rate dischargeability at the discharge current density of 1200 mA/g first increased from 52.1% (x=0) to 59.1% (x=0.15), and then decreased to 55.4% (x=0.20). The hydrogen diffusion in the bulky alloy was responsible for the high-rate dischargeability. Cycling stability first increased with increasing x from 0 to 0.10 and then decreased when x increased to 0.20, which was resulted from the synthesized effect of the improvement of the pulverization resistance and the decrease of corrosion resistance.
