2025 SPECIAL ISSUE ON SOLID-STATE HYDROGEN STORAGE MATERIALS: EXPERT FORUM
LUO Yongchun, JIN Tianfu, LEI Ming, XIE Yunding, MA Zhewen
Hydrogen storage alloy as an anode material has an important influence on the performance of Ni-MH secondary batteries. To further improve the cycling stability of hydrogen storage alloy electrode materials with RE-Mg-Ni system superlattice structure, Mg-free A5B19 Gd1-xSmxNi3.33Mn0.17Co0.2Al0.1 0≤x≤1 alloy was designed and investigated. The effects of the substitution of Gd by the rare-earth Sm element on the alloy′s annealing microstructure, hydrogen storage in the gas, and electrochemical properties were systematically investigated. The results show that after annealing at 1 273 K, the alloy microstructure consists of 2H-Ce2Ni7-type main phase and 3R-Ce5Co19-type dual phase. With the increase of Sm content x, the abundance of 2H-Ce2Ni7-type main phase increases, and the 3R-Ce5Co19-type phase gradually decreases. Meanwhile, the cellular parameters a, c, V of the 2H-Ce2Ni7-type phase and the 3R-Ce5Co19-type phase all increase gradually with increasing Sm content. The effect of rare earth Sm on the gas hydrogenation behavior of the alloys is more pronounced. After the addition of Sm, the alloys exhibit a certain tendency of hydrogen-induced amorphization during hydrogen absorption and desorption. With the increase of Sm content, the maximum hydrogen absorption capacity of the alloys gradually increases, and the PCT curve platform for hydrogen storage and the enthalpy of formation of alloy hydrides of ΔHΘ are significantly reduced. The electrodes of the alloys containing Sm exhibit good charge/discharge activation properties. With the increase of Sm content, the discharge capacity of the electrodes increases from 279.6 mAh/g to 378.4 mAh/g at x=1.0. After 100 charge/discharge cycles, the alloy electrodes maintain good capacity retention S100 = 94.3%-98.8%, with a slight decrease in capacity retention rate as Sm content increases. When Sm content x > 0, the alloy electrodes exhibit good high-current discharge performance, with HRD900 values ranging from 84.7% to 87.6%, respectively. The x = 1.0 alloy combines a high discharge capacity 378.4 mAh/g, good cycling stability S100=94.3%, and high-rate discharge performance HRD900 = 84.7%, demonstrating excellent overall electrochemical properties.