In this paper, the Co-free hydrogen storage alloys with the nominal compositions of La0.75R0.05Mg0.20Ni3.40Al0.10(R = La, Nd and Sm) were prepared by induction melting, and then the phase structure and electrochemic...In this paper, the Co-free hydrogen storage alloys with the nominal compositions of La0.75R0.05Mg0.20Ni3.40Al0.10(R = La, Nd and Sm) were prepared by induction melting, and then the phase structure and electrochemical properties of these alloys were comparatively investigated. It is found that the alloys mainly consist of(La, Mg)2Ni7phase, La Ni5 phase and(La, Mg)5Ni19phase.Refinement results further show that Nd substitution for La remarkably promotes the formation of La Ni5 phase, while Sm is beneficial for the formation of(La, Mg)5Ni19phase.At discharge current density of 1,875 m A g-1, the highrate dischargeability(HRD) of alloy electrodes increases by 13.9 % and 6.5 % with La substituted by Nd and Sm,respectively. The electrochemical kinetic measurements reveal that the exchange current density(I0), charge transfer resistance(R) and hydrogen diffusion coefficient(D) for the alloy electrode are all facilitated with Nd and Sm partial substitution for La. Subsequently, a linear correlation between the HRD1875 and the corresponding I0/D is found.展开更多
The present work focuses on the structural stability upon hydrogenation of three typical La-Mg-Ni-based alloys: La2 MgNi9, LaaMgNi14 and La4MgNi19. Structural changes during gaseous and electrochemical cycles were ch...The present work focuses on the structural stability upon hydrogenation of three typical La-Mg-Ni-based alloys: La2 MgNi9, LaaMgNi14 and La4MgNi19. Structural changes during gaseous and electrochemical cycles were characterized, and the influence of the structure distortion on the hydrogen storage properties was concerned. Hydrogen-induced amor- phization (HIA) and disproportionation of the three alloys have occurred during both the gaseous and electrochemical cycles. Structural stability of the phase structures in the La-Mg-Ni system is found to follow the order: LaNi5- 〉 (La,Mg)5Ni19 〉 (La,Mg)2Ni7 〉 (La,Mg)Ni3 〉 (La,Mg)Ni2. HIA increases thermal stability of the metal hydrides and difficulty to dehydrogenation and leads to degradation of both the gaseous and electrochemical capacities. Interestingly, LaEMgNi9 with poor stability presents elevated discharge capability even at 60 ℃ which can be attributed to increase in the hydrogen desorption capability and inhibition of the self-discharge induced by severe HIA at higher temperatures. In addition, HIA in the electrochemical reactions is obviously weaker than the extent during the gaseous cycles, which is mainly due to the slower hydrogenation speed. The development of HIA in the gaseous and electrochemical process is considered to follow the direct and gradual modes, respectively.展开更多
利用扫描电镜(SEM)、X射线衍射(XRD)等检测分析稀土元素La对Mg-6%Al-5%Pb(AP65)镁合金(质量分数)显微组织的影响,并采用恒电流法、动电位极化扫描法和析氢法研究La含量对AP65镁合金的腐蚀电化学性能的影响。结果表明:加入La能够使AP65...利用扫描电镜(SEM)、X射线衍射(XRD)等检测分析稀土元素La对Mg-6%Al-5%Pb(AP65)镁合金(质量分数)显微组织的影响,并采用恒电流法、动电位极化扫描法和析氢法研究La含量对AP65镁合金的腐蚀电化学性能的影响。结果表明:加入La能够使AP65镁合金α-Mg组织得到细化,生成针状稀土相Mg80(Al,La)17和块状稀土相Mg17(Al,La)12;添加La提高了AP65镁合金的电化学活性、耐腐蚀性能和阳极效率,使AP65的平均电位负移;当La含量为2%(质量分数)时,平均电位最负为-1.73 V(vs SCE)。添加6%La使AP65镁合金的平均析氢速率从1.75 m L/(cm2·h)下降到0.02 m L/(cm2·h),并且使阳极效率从74.30%上升到82.31%。展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 51171165 and 21303157)the Natural Science Foundation of Hebei Province (Nos. B2012203027, B2012203104, and B2014203114)+1 种基金the China Postdoctoral Science Foundation Project (No. 2013M541201)the Research Fund for the Doctoral Program of Higher Education of China (No. 20131333120008)
文摘In this paper, the Co-free hydrogen storage alloys with the nominal compositions of La0.75R0.05Mg0.20Ni3.40Al0.10(R = La, Nd and Sm) were prepared by induction melting, and then the phase structure and electrochemical properties of these alloys were comparatively investigated. It is found that the alloys mainly consist of(La, Mg)2Ni7phase, La Ni5 phase and(La, Mg)5Ni19phase.Refinement results further show that Nd substitution for La remarkably promotes the formation of La Ni5 phase, while Sm is beneficial for the formation of(La, Mg)5Ni19phase.At discharge current density of 1,875 m A g-1, the highrate dischargeability(HRD) of alloy electrodes increases by 13.9 % and 6.5 % with La substituted by Nd and Sm,respectively. The electrochemical kinetic measurements reveal that the exchange current density(I0), charge transfer resistance(R) and hydrogen diffusion coefficient(D) for the alloy electrode are all facilitated with Nd and Sm partial substitution for La. Subsequently, a linear correlation between the HRD1875 and the corresponding I0/D is found.
基金supported financially by the National Natural Science Foundation of China (No.51761032)the University Foundation of Inner Mongolia (No.NJZZ18142)
文摘The present work focuses on the structural stability upon hydrogenation of three typical La-Mg-Ni-based alloys: La2 MgNi9, LaaMgNi14 and La4MgNi19. Structural changes during gaseous and electrochemical cycles were characterized, and the influence of the structure distortion on the hydrogen storage properties was concerned. Hydrogen-induced amor- phization (HIA) and disproportionation of the three alloys have occurred during both the gaseous and electrochemical cycles. Structural stability of the phase structures in the La-Mg-Ni system is found to follow the order: LaNi5- 〉 (La,Mg)5Ni19 〉 (La,Mg)2Ni7 〉 (La,Mg)Ni3 〉 (La,Mg)Ni2. HIA increases thermal stability of the metal hydrides and difficulty to dehydrogenation and leads to degradation of both the gaseous and electrochemical capacities. Interestingly, LaEMgNi9 with poor stability presents elevated discharge capability even at 60 ℃ which can be attributed to increase in the hydrogen desorption capability and inhibition of the self-discharge induced by severe HIA at higher temperatures. In addition, HIA in the electrochemical reactions is obviously weaker than the extent during the gaseous cycles, which is mainly due to the slower hydrogenation speed. The development of HIA in the gaseous and electrochemical process is considered to follow the direct and gradual modes, respectively.
文摘利用扫描电镜(SEM)、X射线衍射(XRD)等检测分析稀土元素La对Mg-6%Al-5%Pb(AP65)镁合金(质量分数)显微组织的影响,并采用恒电流法、动电位极化扫描法和析氢法研究La含量对AP65镁合金的腐蚀电化学性能的影响。结果表明:加入La能够使AP65镁合金α-Mg组织得到细化,生成针状稀土相Mg80(Al,La)17和块状稀土相Mg17(Al,La)12;添加La提高了AP65镁合金的电化学活性、耐腐蚀性能和阳极效率,使AP65的平均电位负移;当La含量为2%(质量分数)时,平均电位最负为-1.73 V(vs SCE)。添加6%La使AP65镁合金的平均析氢速率从1.75 m L/(cm2·h)下降到0.02 m L/(cm2·h),并且使阳极效率从74.30%上升到82.31%。