La-Mg-Ni system (PuNi3-type) hydrogen storage alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Fe, Cu, Al; x=0, 0.1) were prepared by casting and rapid quenching. Aiming to improve the cycle stabilities of the alloys, Ni in the alloy was partly substituted by Fe, Cu and Al. The effects of the substitution of Fe, Cu and Al for Ni and the rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM indicate that the element substitution has no influence on the phase compositions of the alloys, but it changes the phase abundances of the alloys. Particularly, the substitution of Al and Cu obviously increases the amount of the LaNi2 phase. The substitution of Al and Fe leads to a great refinement of the as-quenched alloy′s grains. The substitution of Al strongly restrains the formation of the amorphous in the as-quenched alloy, but the substitution of Fe and Cu is quite helpful for the formation of an amorphous phase. The effects of the substitution of Fe, Cu and Al on the cycle stabilities of the as-cast and quenched alloys are different. The positive impact of the substitution elements on the cycle stabilities of the as-cast alloys is ranked in proper order Al>Fe>Cu, and for as-quenched alloys, the order is Fe>Al>Cu. Rapid quenching engenders an unconscious influence on the phase composition, but it markedly enhances the cycle stabilities of the alloys.
The La0.7Mg0.3Ni2.55-xCo0.45Cux (x=0, 0.1, 0.2, 0.3, 0.4) electrode alloys were prepared by casting and rapid quenching. Ni in the alloy was partially substituted by Cu in order to improve the cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy. The effects of substituting Ni with Cu on the microstructures and cycle stability of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM show that the substitution of Cu for Ni is favourable for the formation of an amorphous in the as-quenched alloy, and this leads to an obvious refinement of the as-quenched alloy grains and a growth of the lattice constants and cell volumes of the as-cast and quenched alloys. The results obtained by the electrochemical measurement indicate that the cycle stability of the alloys significantly rises with the incremental variety of Cu content. When Cu content changes from 0 to 0.4, the cycle lives of the as-cast and quenched (30 m/s) alloys are enhanced from 72 to 88 cycles and from 100 to 121 cycles, respectively.
In order to investigate the influences of the stoichiometric ratio of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structures and electrochemical performances of the AB3.5-4.1-type electrode alloys, the La-Mg-Ni-Co system La0.75Mg0.25Ni3.5Mx (M=Ni, Co; x= 0, 0.2, 0.4, 0.6) alloys were prepared by induction melting in a helium atmosphere. The structures and electrochemical performances of the alloys were systemically measured. The results show that the structures and electrochemical performances of the alloys are closely relevant to the B/A ratio. All the alloys exhibit a multiphase structure, including two major phases, (La, Mg)2Ni7 and LaNi5, and a residual phase LaNi2, and with rising ratio B/A, the (La,Mg)2Ni7 phase decreases and the LaNi5 phase increases significantly. When ratio B/A=3.7, the alloys obtain the maximum discharge capacities. The high rate discharge(HRD) capability of the alloy (M=Ni) monotonously rises with growing B/A ratio, but that of the alloy (M=Co) first mounts up then declines. The cycle stability of the alloy (M=Co) monotonously increases with rising B/A ratio, but it first decreases slightly then increases for the alloy (M=Ni). The discharge potential of the alloy (M=Ni) declines with increasing B/A ratio (x>0.2), but for the alloy (M=Co), the result is contrary. The substitution of Co for Ni significantly ameliorates the electrochemical performances. For a fixed ratio B/A=3.7, the Co substitution enhances the discharge capacity from 365.7 to 401.8 mA·h/g, the capacity retention ratio (S100) after 100 charging-discharging cycles from 50.32% to 53.26% and the HRD from 88.65% to 90.69%.
Aiming at the improvement of the cyclic stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloy was partly substituted by Fe. The electrode alloys of La0.7Mg0.3Co0.45Ni2.55-xFex (x=0, 0.1, 0.2, 0.3, 0.4) were prepared by casting and rapid quenching. The influence of the quenching on cyclic stability as well as structure of the alloys was investigated in detail. The results of elec- trochemical measurement indicated that rapid quenching significantly improved cyclic stability. When the quenching rate rose from 0 (As-cast was defined as a quenching rate of 0 m/s) to 30 m/s, the cyclic life of Fe-free alloy (x=0) increased from 81 to 105 cycles, and for alloy containing Fe(x=0.4), it grew from 106 to 166 cycles at a current density of 600 mA/g. The results obtained by XRD, TEM and SEM revealed that the as-cast and quenched alloys had multiphase structures, including two major phases (La, Mg)Ni3 and LaNi5 as well as an impurity phase LaNi2. Rapid quenching helped the formation of an amorphous-like structure in Fe containing alloys.
