Authors: Yang Huan Zhang, Ying Cai, Tai Yang, Zhong Hui Hou, Guo Fang Zhang, Dong Liang Zhao
Abstract: The Mg2Ni-type alloys with a nanocrystalline and amorphous structure have been confirmed possessing superior electrochemical hydrogen storage kinetics. The melt-spinning technique is used to preparing the nanocrystalline and amorphous Mg2Ni-type alloys with the nominal compositions of Mg20Ni10-xMnx (x = 0, 1, 2, 3, 4). The impacts of the melt spinning and the replacement of Ni by Mn on the structures and the electrochemical performances of the alloys are investigated systematically. The analysis of the structures by XRD and HRTEM reveals that the replacement of Ni by Mn facilitates the glass formation in the Mg2Ni-type alloy, and the amorphization degree of the as-spun alloys increases with the growing of the spinning rate. Furthermore, the replacement renders the formation of secondary phases MnNi and Mg instead of altering the Mg2Ni major phase in the alloys. The measurement of the electrochemical characteristics by an automatic galvanostatic system indicates that the discharge capacity and cycle stability of the alloys dramatically grow with the rising of the spinning rate and the amount of Mn replacement, with which the high rate discharge ability (HRD) of the alloys first augments and then falls.
323
Authors: Yang Huan Zhang, Hong Wei Shang, Guo Fang Zhang, Tai Yang, Zhong Hui Hou, Dong Liang Zhao
Abstract: The melt-spinning technique was used to synthesize the Mg20Ni6M4 (M=Co, Cu) alloys with nanocrystalline and amorphous structure. The microstructures of the as-spun alloys were characterized by XRD and TEM. The electrochemical hydrogen storage properties of the alloys were measured. The results show that the as-spun (M=Cu) alloys hold an entire nanocrystalline structure, whereas the as-spun (M=Co) alloys display a nanocrystalline and amorphous structure, confirming that the substitution of Co for Ni facilitates the glass formation in the Mg2Ni-type alloy. The discharge capacity and high rate discharge ability (HRD) of the alloys notably augment with the rising of the spinning rate. The action of the melt spinning on the cycle stability of the alloys is associated with the substitution element. For the (M=Co) alloy, the melt spinning exerts a dramatically positive impact, whereas for the (M=Cu) alloy, its impact is negative.
3
Authors: Yang Huan Zhang, Hui Ping Ren, Bao Wei Li, Zhong Hui Hou, Guo Fang Zhang, Dong Liang Zhao
Abstract: The Ni was partially substituted by M (M=Co, Cu) in order to ameliorate the hydriding and dehydriding kinetics of Mg2Ni-type alloy. The melt spinning technology was used to prepare the Mg20Ni10-xMx (M=Mn, Cu; x=0, 1, 2, 3, 4) alloys. The structures of the as-spun alloys were characterized by XRD and TEM. The hydriding and dehydriding kinetics of the alloys were measured by an automatically controlled Sieverts apparatus. The results show that the as-spun (M=Mn) alloys hold a nanocrystalline and amorphous structure, whereas the as-spun (M=Cu) alloys display an entire nanocrystalline structure, indicating that the substitution of Mn for Ni facilitates the glass formation in the Mg2Ni-type alloy. Additionally, Mn substitution incurs the formation of secondary phases MnNi and Mg instead of changing the Mg2Ni major phase. The hydriding kinetics of the as-spun alloys first mounts up and then declines with the rising of M (M= Mn, Cu) content, whereas the substitution of M (M=Mn, Cu) for Ni enhances the dehydriding kinetics of the alloy dramatically.
1347
Authors: Zhong Hui Hou, Yin Zhang, Ying Cai, Feng Hu, Guo Fang Zhang, Xia Li
Abstract: The melt spinning technology was used to prepare the Mg2Ni0.6M0.4 (M=Cu, Co) hydrogen storage alloys in order to obtain a nanocrystalline and amorphous structure. The microstructures of the alloys were characterized by XRD, TEM. The effects of the melt spinning on the electrochemical and gaseous hydrogen storage capacities of the alloys were investigated. The results indicate that the as-spun (M=Cu) alloys hold an entire nanocrystalline structure even if a limited spinning rate is applied, while the as-spun (M=Co) alloys display a nanocrystalline and amorphous structure and the amount of the amorphous phase grows evidently with the rising of the spinning rate, suggesting that the substitution of Co for Ni facilitates the glass formation in the Mg2Ni-type alloy. The melt spinning enhances the electrochemical and gaseous hydrogen storage capacities of the alloys dramatically. Simultaneously, it ameliorates the hydriding kinetics of the alloys substantially. As the spinning rate grows from 0 (As-cast was defined as the spinning rate of 0 m/s) to 30 m/s, the discharge capacity increases from 53.3 to 140.4 mAh/g for the (M=Cu) alloy and from 113.3% to 402.5% for the (M=Co) alloy; the gaseous hydrogen desorption capacity ( ) in 100 min augments from 2.29% to 2.87% for the (M=Cu) alloy and from 2.42% to 3.08% for the (M=Co) alloy.
382
Authors: Yang Huan Zhang, Hong Wei Shang, Guo Fang Zhang, Tai Yang, Zhong Hui Hou, Dong Liang Zhao
Abstract: The melt-spinning technique is used to fabricate the Mg20Ni9M1 (M=Cu, Co) alloys with nanocrystalline and amorphous structure. The microstructures of the as-spun alloys were characterized by XRD and TEM. The electrochemical hydrogen storage properties of the alloys were measured. The results show that the as-spun (M=Cu) alloys hold an entire nanocrystalline structure and small amount of amorphous phase is visible on the grain boundaries of the as-spun (M=Co) alloy. The discharge capacity and high rate discharge ability (HRD) of the alloys visibly grow with the rising of the spinning rate. The action of the melt spinning on the cycle stability of the alloys is associated with substitution element. For M=Cu, the capacity retaining rate (SN) evidently falls with the growing of the spinning rate; whereas for M=Co, it first declines and then augments.
405
Authors: Yang Huan Zhang, Guo Fang Zhang, Xiao Gang Liu, Le Le Chen, Zhong Hui Hou, Dong Liang Zhao
Abstract: The poor electrochemical cycle stability of Re-Mg-Ni system A2B7-type electrode alloys has limited their practical application as the negative electrode materials of Ni-MH battery. In order to improve the electrochemical cycle stability of the La-Mg-Ni system A2B7-type electrode alloys, the partial substitution of Zr for La has been performed. The La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1 (x = 0–0.2) electrode alloys were fabricated by casting and melt-spinning. The microstructures and the electrochemical cycle stability and kinetics of the alloys were investigated. The structure characterized by XRD, SEM and HRTEM reveals that the as-cast and spun alloys have a multiphase structure, composing of two main phases (La, Mg)2Ni7 and LaNi5 as well as a residual phase LaNi2. The as-spun Zr-free alloy displays an entire nanocrystalline structure, but a like amorphous structure is detected in the as-spun alloy substituted by Zr, suggesting that the substitution of Zr for La facilitates the formation of an amorphous structure. The electrochemical measurement indicates that both the substitution of Zr for La and the melt spinning remarkably ameliorate electrochemical cycle stability of the alloys. Furthermore, the high rate discharge ability (HRD), the electrochemical impedance spectrum (EIS) and the potential-step measurements all indicate that both of the melt spinning and the Zr substitution bring on a notable decline of the electrochemical kinetics of the alloys.
1016
Authors: Yang Huan Zhang, Chao Xu, Tai Yang, Zhong Hui Hou, Guo Fang Zhang, Dong Liang Zhao
Abstract: The melt-spinning technique is applied to the preparation of the nanocrystalline and amorphous Mg2Ni-type alloys with nominal compositions of Mg20Ni10-xMnx (x=0, 1, 2, 3, 4). The microstructures of the as-cast and spun alloys were characterized by XRD and HRTEM. The electrochemical performances of the as-spun alloys are measured by an automatic galvanostatic system. The results show that the as-spun Mg20Ni10 alloy displays an entire nanocrystalline structure, whereas the as-spun Mg20Ni6Mn4 alloy exhibits a nanocrystalline and amorphous structure, confirming that the substitution of Mn for Ni facilitates the glass formation in the Mg2Ni-type alloy. And the amorphization degree of the as-spun alloys substituted by Mn increases with the growing of the spinning rate. The substitution of Mn for Ni and the melt spinning ameliorate electrochemical hydrogen storage characteristics of the alloys substantially. The electrochemical discharge capacity and cycle stability of the alloys are considerably enhanced by increasing the amount of Mn substitution and the spinning rate. The high rate discharge ability (HRD) of the alloys first augments and then falls with the growing of the Mn content and the spinning rate.
1169
Authors: Yang Huan Zhang, Zhong Hui Hou, Guo Fang Zhang, Hong Wei Shang, Feng Hu, Dong Liang Zhao
Abstract: In order to obtain a nanocrystalline and amorphous structure in the Mg2Ni-type alloy, the Ni in Mg2Ni alloy has been partially substituted by M (M=Co, Cu), and the melt spinning has been used to fabricate the Mg20Ni10-xMx (M=Co, Cu; x=0-4) hydrogen storage alloys. The microstructures of the alloys were characterized by XRD, SEM and HRTEM. The effects of substituting Ni with M (M=Co, Cu) on the gaseous and electrochemical hydrogen storage kinetics of the as-spun alloys were investigated. The results indicate that the as-spun (M=Co) alloys display a nanocrystalline and amorphous structure, while the as-spun (M=Cu) alloys hold an entire nanocrystalline structure, suggesting that the substitution of Co for Ni facilitates the glass formation in the Mg2Ni-type alloy. The substitution of M (M=Co, Cu) for Ni exerts a trifling impact on the hydriding kinetics of the alloys, but it renders a marked enhancement of dehydriding capacity and kinetics. Furthermore, the measurements of the high rate discharge ability (HRD) and the hydrogen diffusion coefficient (D) as well as the electrochemical impedance spectra (EIS) of the alloys exhibit that the electrochemical kinetics of the as-spun (30 m/s) alloys is significantly ameliorated by substituting Ni with M (M=Co, Cu).
43
Authors: Zhong Hui Hou, Guo Fang Zhang, Xia Li, Feng Hu, Yin Zhang, Ying Cai, Yang Huan Zhang
Abstract: The poor electrochemical cycle stability of RE–Mg–Ni system A2B7-type electrode alloys have limited their practical application as the negative electrode materials of Ni–MH battery. In order to improve the electrochemical cycle stability of the La–Mg–Ni system A2B7-type electrode alloys, the partial substitution of Pr for La has been performed. The La0.75−xPrxMg0.25Ni3.2Co0.2Al0.1 (x = 0–0.4) electrode alloys were fabricated by casting and melt-spinning. The microstructures and electrochemical cycle stability of the as-cast and spun alloys were investigated by XRD, SEM and HRTEM. The results show that the as-cast and spun alloys have a multiphase structure, consisting of two main phases (La, Mg)2Ni7 and LaNi5 as well as a residual phase LaNi2. The substitution of Pr for La brings on a notable grain refinement of the as-cast alloys instead of altering the phase structure of the alloys. The electrochemical measurement indicates that the cycle stability of the alloy remarkably grows with increasing both Pr content and spinning rate. The substitution of Pr for La and the melt spinning significantly ameliorate electrochemical cycle stability of the alloys. The capacity retaining rate (S100) of the as-spun (15 m/s) alloys at 100th charging/discharging cycle is enhanced from 72.38% to 90.33% by increasing Pr content from 0 to 0.4. And that of the Pr0.3 alloy is increased from 78.11% to 92.32% by growing spinning rate from 0 (as-cast was defined as the spinning rate of 0 m/s) to 20 m/s.
1634
Authors: Yang Huan Zhang, Guo Fang Zhang, Hong Wei Shang, Zhong Hui Hou, Ying Cai, Dong Liang Zhao
Abstract: It was well known that the Mg2Ni-type alloy with a nanocrystalline/amorphous structure possesses superior hydrogen storage kinetics. In order to obtain a nanocrystalline and amorphous structure, the melt spinning was applied to prepare the Mg2Ni-type Mg20Ni6M4 (M=Cu, Co) hydrogen storage alloys. The microstructures of the as-cast and spun alloys were characterized by XRD, SEM and HRTEM. The gaseous hydriding and dehydriding kinetics of the alloys was measured. The results show that the as-spun (M=Co) alloys display a nanocrystalline and amorphous structure as spinning rate approaches to 20 m/s, while the as-spun (M=Cu) alloys hold an entire nanocrystalline structure whatever spinning rate is, suggesting that the substitution of Co for Ni facilitates the glass formation in the Mg2Ni-type alloy. The melt spinning markedly improves the gaseous hydrogen storage kinetics of the alloys. As the spinning rate grows from 0 (as-cast was defined as the spinning rate of 0 m/s) to 30 m/s, the hydrogen absorption saturation ratio ( ) is enhanced from 57.7% to 91.4% for the (M=Cu) alloy and from 77.1% to 93.5% for the (M=Co) alloy. And hydrogen desorption ratio ( ) is raised from 28.7% to 59.0% for the (M=Cu) alloy and from 54.5% to 70.2% for the (M=Co) alloy, respectively.
1389