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） alloys 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 lattice 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 100^th cycle （$10o） 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
La0.7Ce0.3Ni3.75Mn0.35Al0.15Cu0.75-xFex （x=0-0.20） hydrogen storage alloys were synthesized by induction melting and subsequent annealing treatment, and phase structure and electrochemical characteristics were investigated. All alloys consist of a single LaNi5 phase with CaCu5 structure, and the lattice constant a and the cell volume （V） of the LaNi5 phase increase with increasing x value. The maximum discharge capacity gradually decreases from 319.0 mA？h/g （x=0） to 291.9 mA？h/g （x=0.20） with the increase in x value. The high-rate dischargeability at the discharge current density of 1200 mA/g decreases monotonically from 53.1% （x=0） to 44.2% （x=0.20）. The cycling stability increases with increasing x from 0 to 0.20, which is mainly ascribed to the improvement of the pulverization resistance.
LaFeO3 was used to improve the hydrogen storage properties of Mg H2. The Mg H2＋20 wt.%La Fe O3 composite was prepared by ball milling method. The composite could absorb 3.417 wt.% of hydrogen within 21 min at 423 K while Mg H2 only uptaked 0.977 wt.% hydrogen under the same conditions. The composite also released 3.894 wt.% of hydrogen at 623 K, which was almost twice more than Mg H2. The TPD measurement showed that the onset dissociation temperature of the composite was 570 K, 80 K lower than the Mg H2. Based on the Kissinger plot analysis of the composite, the activation energy E des was estimated to be 86.69 k J/mol, which was 36 k J/mol lower than Mg H2. The XRD and SEM results demonstrated that highly dispersed La Fe O3 could be presented in Mg H2, benefiting the reduction of particle size and also acting as an inhibitor to keep the particles from clustering during the ball-milled process.
