Nanocrystalline and amorphous LaMg_（12）-type LaMg_（11）Ni ＋ x wt% Ni（x = 100, 200） alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydroge...Nanocrystalline and amorphous LaMg_（12）-type LaMg_（11）Ni ＋ x wt% Ni（x = 100, 200） alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter（DSC） connected with a H_2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability（HRD） and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.展开更多
The nanocrystalline and amorphous LaMg11Ni ＋ x wt% Ni （x = 100, 200） composites were synthesized by the mechanical milling, and their gaseous and electrochemical hydrogen storage kinetics performance were systemati...The nanocrystalline and amorphous LaMg11Ni ＋ x wt% Ni （x = 100, 200） composites were synthesized by the mechanical milling, and their gaseous and electrochemical hydrogen storage kinetics performance were systematically investigated, The results indicate that the as-milled composites exhibit excellent hydrogen storage kinetic performances, and increasing Ni content significantly facilitates the improvement of the hydrogen storage kinetics properties of the composites. The gaseous and electrochemical hydrogen storage kinetics of the composites reaches a maximum value with the variation of milling time. Increasing Ni content and milling time both make the hydrogen desorption activation energy lower, which are responsible for the enhancement in the hydrogen storage kinetics properties of the composites. The diffusion coefficient of hydrogen atom and activation enthalpy of charge transfer on the surface of the as-milled composites were also calculated, which are considered to be the dominated factors for the electrochemical high rate discharge ability.展开更多
Nanocrystalline/amorphous LaMg(12)-type alloyNi composites with a nominal composition of LaMg(11)Ni+x wt% Ni(x=100,200) were synthesized by mechanical milling.Effects of Ni content and milling time on the gaseous hydr...Nanocrystalline/amorphous LaMg(12)-type alloyNi composites with a nominal composition of LaMg(11)Ni+x wt% Ni(x=100,200) were synthesized by mechanical milling.Effects of Ni content and milling time on the gaseous hydrogen storage thermodynamics and dynamics of alloys were systematically investigated.The hydrogen desorption properties were studied by Sievert apparatus and a differential scanning calorimeter(DSC).Thermodynamic parameters(△H and ΔS) for the hydrogen absorption and desorption of alloys were calculated by Van't Hoff equation.Hydrogen desorption activation energy of alloy hydride was estimated by Arrhenius and Kissinger methods.The increase in Ni content has a slight effect on the thermodynamic properties of alloys,but it significantly enhances the hydrogen absorption and desorption kinetics performance of alloys.Moreover,variation of milling time clearly affects the hydrogen storage properties of alloys.Hydrogen absorption capacity(C(100)~a) and hydrogen absorption saturation ratio(R(10)~a)(a ratio of the hydrogen absorption capacity at 10 min to the saturated hydrogen absorption capacity) have maximum values with milling time varying.But hydrogen desorption ratio(R(20)~d)(a ratio of the hydrogen desorption capacity at 20 min to the saturated hydrogen absorption capacity) always increases with milling time prolonging.Particularly,prolonging milling time from 5 to 60 h makes R(20)~d increase from 10.89% to 16.36% for the x=100 alloy and from 13.93% to 21.68% for the x=200 alloy,respectively.展开更多
To improve the hydrogen storage performance of CeMg12-type alloys, partially substituting Mg with Ni in the alloy was conducted. The way to synthesize the target alloy powders was the mechanical milling method, by whi...To improve the hydrogen storage performance of CeMg12-type alloys, partially substituting Mg with Ni in the alloy was conducted. The way to synthesize the target alloy powders was the mechanical milling method, by which the CeMg11-Ni ＋ x wt% Ni （x = 100, 200） alloy powders with nanocrystalline and amorphous structure were obtained. The influence of the milling time and Ni content on the hydrogen storage properties of the alloys was discussed. The X-ray diffractometer and high-resolution transmission electron microscope were used to investigate the microstructures of the ball-milled alloys. The hydrogenation/dehydrogenation dynamics were studied using a Sievert instrument and a differential scanning calorimeter which was linked with a H2 detector. The hydrogen desorption activation energies of the alloy hydrides were evaluated by Arrhenius and Kissinger equations. From the results point of views, there is a little decline in the thermo- dynamic parameters （enthalpy and entropy changes） with the increase in Ni content. However, the alloys desorption and absorption dynamics are improved distinctly. What is more, the variation of milling time results in a dramatic influence on the hydrogen storage performances of alloys. Various maximum values of the hydrogen capacities correspond to different milling time, which are 5.805 and 6.016 wt% for the CeMgllNi ＋ x wt% Ni （x = 100, 200） alloys, respectively. The kinetics tests suggest that the hydrogen absorption rates increase firstly and then decrease with prolonging the milling time. The improvement of the gaseous hydrogen storage kinetics results from the decrease in the activation energy caused by the increase in Ni content and milling time.展开更多
Nanocrystalline and amorphous Nd Mg_（12^-）type Nd Mg_（11）Ni＋ x wt% Ni（x=100, 200） hydrogen storage alloys were synthesized by mechanical milling. The effects of Ni content and milling time on hydrogen storage t...Nanocrystalline and amorphous Nd Mg_（12^-）type Nd Mg_（11）Ni＋ x wt% Ni（x=100, 200） hydrogen storage alloys were synthesized by mechanical milling. The effects of Ni content and milling time on hydrogen storage thermodynamics and dynamics of the alloys were systematically investigated. The gaseous hydrogen absorption and desorption properties were investigated by Sieverts apparatus and differential scanning calorimeter connected with a H_2 detector. Results show that increasing Ni content significantly improves hydrogen absorption and desorption kinetics of the alloys. Furthermore,varying milling time has an obvious effect on the hydrogen storage properties of the alloys. Hydrogen absorption saturation ratio（R^a_（10）; a ratio of the hydrogen absorption capacity in 10 min to the saturated hydrogen absorption capacity） of the alloys obtains the maximum value with varying milling time. Hydrogen desorption ratio（R^d_（20）, a ratio of the hydrogen desorption capacity in 20 min to the saturated hydrogen absorption capacity） of the alloys always increases with extending milling time. The improved hydrogen desorption kinetics of the alloys are considered to be ascribed to the decreased hydrogen desorption activation energy caused by increasing Ni content and milling time.展开更多
To improve the hydrogen storage performance of PrMg12-type alloys, Ni was adopted to replace partially Mg in the alloys. The PrMgllNi＋x wt.% Ni （x=100, 200） alloys were prepared via mechanical milling. The phase st...To improve the hydrogen storage performance of PrMg12-type alloys, Ni was adopted to replace partially Mg in the alloys. The PrMgllNi＋x wt.% Ni （x=100, 200） alloys were prepared via mechanical milling. The phase structures and morphology of the experimental alloys were in vestigated by X-ray diffraction and transmission electron microscopy. The results show that increasing milling time and Ni content accelerate the formation of nanocrystalline and amorphous structure. The gaseous hydrogen storage properties of the experimental alloys were determined by differential scanning calorimetry （DSC） and Sievert apparatus. In addition, increasing milling time makes the hydrogenation rates of the alloys augment firstly and decline subsequently and the dehydrogenation rate always increases. The maximum capacity is 5. 572 wt. % for the x = 100 alloy and 5. 829 wt. % for the x = 200 alloy, respectively. The enthalpy change （ △H ）, entropy change （△S） and the dehydrogenation activation energy （Exde） markedly lower with increasing the milling time and the Ni content due to the generation of nanocrystalline and amorphous structure.展开更多
Nanocrystalline and amorphous NdMg12-type NdMg11Ni+x wt%Ni(x=100,200)alloys were successfully prepared through ball milling(BM).The microstructures and electrochemical properties were systematically studied to get a m...Nanocrystalline and amorphous NdMg12-type NdMg11Ni+x wt%Ni(x=100,200)alloys were successfully prepared through ball milling(BM).The microstructures and electrochemical properties were systematically studied to get a more comprehensive understanding of the sample alloys.The maximum discharging capacity could be obtained at only two cycles,indicating that as-milled alloys have superior activation capability.The more the Ni content,the better the electrochemical properties of the as-milled samples.To be specific,the discharge capacities of x=100 and x=200(BM 20 h)samples are 128.2 and 1030.6 mAh/g at 60 mAh/g current density,respectively,revealing that enhancement of Ni content could significantly improve the discharging capacities of the samples.Additionally,milling duration obviously influences the electrochemical properties of the samples.The discharging capacity always rises with milling duration prolonging for the x=100 sample,but that of the(x=200)sample shows a trend of first augment and then decrease.The cycling stability of the(x=100)alloy clearly decreases with extending milling duration,whereas that of the(x=200)alloy first declines and then augments under the same conditions.In addition,the high rate discharge(HRD)abilities of the sample display the maximal values as milling duration changes.The HRD(HRD=C300/C60×100%)values of the as-milled alloys(x=100,200)are 80.24%and 85.17%,respectively.展开更多
To improve the hydrogenation and dehydrogenation dynamics of NdMg12-type alloy,we replaced part of Mg with Ni in thesamples and used the ball milling method to prepare NdMg11Ni+x wt.%Ni(x=100,200)samples.The infuences...To improve the hydrogenation and dehydrogenation dynamics of NdMg12-type alloy,we replaced part of Mg with Ni in thesamples and used the ball milling method to prepare NdMg11Ni+x wt.%Ni(x=100,200)samples.The infuences of millingduration and Ni content on the electrochemical and gascous dynamics of the samples were studied in detail.Dehydrogena-tion activation cnergies of samples were calculated by using Kissinger and Arrhenius methods.The conclusions show thatthe dynamic properties of samples are significantly enhanced with the increase in Ni content.With the change of the miling duration,the gaseous hydrogenation rate and high rate discharging capability reach the maximal values.However,thedehydrogenation dynamics of sample alloys are always enhanced with the prolonging of milling duration.More concretely,prolonging milling duration from 5 to 60 h improves the dehydrogenation ratio of NdMgNi+100 wt.%Ni alloy from58.03%to 64.81%and that of NdMgNi+200 wt.%Ni alloy from 62.20%to 71.59%.Besides,the enhancement of gaseoushydrogen storage dynamics of the samples is believed to be the result of the declined dehydrogenation activation energyresulted from the increase in milling duration and Ni content.展开更多
To investigate the influence of adding CeO2 on the hydrogen storage characteristics of Sm-Mg-Ni-based SmMg11Ni-type alloy,mechanical milling was utilized to synthesize SrnMg11Ni and SmMg11Ni +5 wt.%CeO2 (named SmMg11N...To investigate the influence of adding CeO2 on the hydrogen storage characteristics of Sm-Mg-Ni-based SmMg11Ni-type alloy,mechanical milling was utilized to synthesize SrnMg11Ni and SmMg11Ni +5 wt.%CeO2 (named SmMg11Ni- 5CeO2)alloys.The microstructure of as-castand as-milled samples was measured via X-ray diffractometer and transmission electron microscope.Sieverts device was utilized to measure the isothermal hydriding and dehydriding kinetics. The non-isothermal dehydrogenation performance was explored by thermogravimetry and differential scanning calorimetry.The hydrogen desorption activation energy of the compound metal hydride can be computed by both Arrhenius and Kissinger methods.The related data show that adding CeO2 can engender a very slight influence on the hydrogen storage thermodynamics,but it can result in an obvious reduction in hydrogen absorption and desorption capacities.Furthermore,the hydrogen desorption performance of experimental alloys is conspicuously ameliorated by the addition of CeO2,viz.lowering the initial hydrogen desorption temperature and enhancing hydrogen desorption rate.The hydrogen desorpfion activation energies with and without CeO2 addition are 84.28 and 100.31 kJ/mol,respectively,with an obvious decrease of 16.03 kJ/mol.This is thought to be responsible for the ameliorated hydrogen desorption kinetics by adding CeO2.展开更多
基金Funded by the National Natural Science Foundation of China(Nos.51471054,51761032,and 51371094)the Natural Science Foundation of Inner Mongolia,China(No.2015MS0558)
文摘Nanocrystalline and amorphous LaMg_（12）-type LaMg_（11）Ni ＋ x wt% Ni（x = 100, 200） alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter（DSC） connected with a H_2 detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability（HRD） and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.
基金financially supported by the National Natural Science Foundation of China (Grant Nos. 51161015 and 51371094)
文摘The nanocrystalline and amorphous LaMg11Ni ＋ x wt% Ni （x = 100, 200） composites were synthesized by the mechanical milling, and their gaseous and electrochemical hydrogen storage kinetics performance were systematically investigated, The results indicate that the as-milled composites exhibit excellent hydrogen storage kinetic performances, and increasing Ni content significantly facilitates the improvement of the hydrogen storage kinetics properties of the composites. The gaseous and electrochemical hydrogen storage kinetics of the composites reaches a maximum value with the variation of milling time. Increasing Ni content and milling time both make the hydrogen desorption activation energy lower, which are responsible for the enhancement in the hydrogen storage kinetics properties of the composites. The diffusion coefficient of hydrogen atom and activation enthalpy of charge transfer on the surface of the as-milled composites were also calculated, which are considered to be the dominated factors for the electrochemical high rate discharge ability.
基金financially supported by the National Natural Science Foundation of China(Nos.51371094 and 51471054)
文摘Nanocrystalline/amorphous LaMg(12)-type alloyNi composites with a nominal composition of LaMg(11)Ni+x wt% Ni(x=100,200) were synthesized by mechanical milling.Effects of Ni content and milling time on the gaseous hydrogen storage thermodynamics and dynamics of alloys were systematically investigated.The hydrogen desorption properties were studied by Sievert apparatus and a differential scanning calorimeter(DSC).Thermodynamic parameters(△H and ΔS) for the hydrogen absorption and desorption of alloys were calculated by Van't Hoff equation.Hydrogen desorption activation energy of alloy hydride was estimated by Arrhenius and Kissinger methods.The increase in Ni content has a slight effect on the thermodynamic properties of alloys,but it significantly enhances the hydrogen absorption and desorption kinetics performance of alloys.Moreover,variation of milling time clearly affects the hydrogen storage properties of alloys.Hydrogen absorption capacity(C(100)~a) and hydrogen absorption saturation ratio(R(10)~a)(a ratio of the hydrogen absorption capacity at 10 min to the saturated hydrogen absorption capacity) have maximum values with milling time varying.But hydrogen desorption ratio(R(20)~d)(a ratio of the hydrogen desorption capacity at 20 min to the saturated hydrogen absorption capacity) always increases with milling time prolonging.Particularly,prolonging milling time from 5 to 60 h makes R(20)~d increase from 10.89% to 16.36% for the x=100 alloy and from 13.93% to 21.68% for the x=200 alloy,respectively.
文摘To improve the hydrogen storage performance of CeMg12-type alloys, partially substituting Mg with Ni in the alloy was conducted. The way to synthesize the target alloy powders was the mechanical milling method, by which the CeMg11-Ni ＋ x wt% Ni （x = 100, 200） alloy powders with nanocrystalline and amorphous structure were obtained. The influence of the milling time and Ni content on the hydrogen storage properties of the alloys was discussed. The X-ray diffractometer and high-resolution transmission electron microscope were used to investigate the microstructures of the ball-milled alloys. The hydrogenation/dehydrogenation dynamics were studied using a Sievert instrument and a differential scanning calorimeter which was linked with a H2 detector. The hydrogen desorption activation energies of the alloy hydrides were evaluated by Arrhenius and Kissinger equations. From the results point of views, there is a little decline in the thermo- dynamic parameters （enthalpy and entropy changes） with the increase in Ni content. However, the alloys desorption and absorption dynamics are improved distinctly. What is more, the variation of milling time results in a dramatic influence on the hydrogen storage performances of alloys. Various maximum values of the hydrogen capacities correspond to different milling time, which are 5.805 and 6.016 wt% for the CeMgllNi ＋ x wt% Ni （x = 100, 200） alloys, respectively. The kinetics tests suggest that the hydrogen absorption rates increase firstly and then decrease with prolonging the milling time. The improvement of the gaseous hydrogen storage kinetics results from the decrease in the activation energy caused by the increase in Ni content and milling time.
基金financially supported by the National Natural Science Foundation of China(Nos.51371094 and 51471054)
文摘Nanocrystalline and amorphous Nd Mg_（12^-）type Nd Mg_（11）Ni＋ x wt% Ni（x=100, 200） hydrogen storage alloys were synthesized by mechanical milling. The effects of Ni content and milling time on hydrogen storage thermodynamics and dynamics of the alloys were systematically investigated. The gaseous hydrogen absorption and desorption properties were investigated by Sieverts apparatus and differential scanning calorimeter connected with a H_2 detector. Results show that increasing Ni content significantly improves hydrogen absorption and desorption kinetics of the alloys. Furthermore,varying milling time has an obvious effect on the hydrogen storage properties of the alloys. Hydrogen absorption saturation ratio（R^a_（10）; a ratio of the hydrogen absorption capacity in 10 min to the saturated hydrogen absorption capacity） of the alloys obtains the maximum value with varying milling time. Hydrogen desorption ratio（R^d_（20）, a ratio of the hydrogen desorption capacity in 20 min to the saturated hydrogen absorption capacity） of the alloys always increases with extending milling time. The improved hydrogen desorption kinetics of the alloys are considered to be ascribed to the decreased hydrogen desorption activation energy caused by increasing Ni content and milling time.
基金financially sponsored by National Natural Science Foundation of China (51471054)
文摘To improve the hydrogen storage performance of PrMg12-type alloys, Ni was adopted to replace partially Mg in the alloys. The PrMgllNi＋x wt.% Ni （x=100, 200） alloys were prepared via mechanical milling. The phase structures and morphology of the experimental alloys were in vestigated by X-ray diffraction and transmission electron microscopy. The results show that increasing milling time and Ni content accelerate the formation of nanocrystalline and amorphous structure. The gaseous hydrogen storage properties of the experimental alloys were determined by differential scanning calorimetry （DSC） and Sievert apparatus. In addition, increasing milling time makes the hydrogenation rates of the alloys augment firstly and decline subsequently and the dehydrogenation rate always increases. The maximum capacity is 5. 572 wt. % for the x = 100 alloy and 5. 829 wt. % for the x = 200 alloy, respectively. The enthalpy change （ △H ）, entropy change （△S） and the dehydrogenation activation energy （Exde） markedly lower with increasing the milling time and the Ni content due to the generation of nanocrystalline and amorphous structure.
基金financially supported by the National Natural Science Foundations of China (Nos. 51761032, 51871125 and 51471054)
文摘Nanocrystalline and amorphous NdMg12-type NdMg11Ni+x wt%Ni(x=100,200)alloys were successfully prepared through ball milling(BM).The microstructures and electrochemical properties were systematically studied to get a more comprehensive understanding of the sample alloys.The maximum discharging capacity could be obtained at only two cycles,indicating that as-milled alloys have superior activation capability.The more the Ni content,the better the electrochemical properties of the as-milled samples.To be specific,the discharge capacities of x=100 and x=200(BM 20 h)samples are 128.2 and 1030.6 mAh/g at 60 mAh/g current density,respectively,revealing that enhancement of Ni content could significantly improve the discharging capacities of the samples.Additionally,milling duration obviously influences the electrochemical properties of the samples.The discharging capacity always rises with milling duration prolonging for the x=100 sample,but that of the(x=200)sample shows a trend of first augment and then decrease.The cycling stability of the(x=100)alloy clearly decreases with extending milling duration,whereas that of the(x=200)alloy first declines and then augments under the same conditions.In addition,the high rate discharge(HRD)abilities of the sample display the maximal values as milling duration changes.The HRD(HRD=C300/C60×100%)values of the as-milled alloys(x=100,200)are 80.24%and 85.17%,respectively.
基金It is sincere thanks to the National Natural Science Foundation of China(Nos.51871125 and 51761032)the MajorScience and Technology Innovation Projects in Shandong Province(2019JZZYO10320)for the financial support of this work.
文摘To improve the hydrogenation and dehydrogenation dynamics of NdMg12-type alloy,we replaced part of Mg with Ni in thesamples and used the ball milling method to prepare NdMg11Ni+x wt.%Ni(x=100,200)samples.The infuences of millingduration and Ni content on the electrochemical and gascous dynamics of the samples were studied in detail.Dehydrogena-tion activation cnergies of samples were calculated by using Kissinger and Arrhenius methods.The conclusions show thatthe dynamic properties of samples are significantly enhanced with the increase in Ni content.With the change of the miling duration,the gaseous hydrogenation rate and high rate discharging capability reach the maximal values.However,thedehydrogenation dynamics of sample alloys are always enhanced with the prolonging of milling duration.More concretely,prolonging milling duration from 5 to 60 h improves the dehydrogenation ratio of NdMgNi+100 wt.%Ni alloy from58.03%to 64.81%and that of NdMgNi+200 wt.%Ni alloy from 62.20%to 71.59%.Besides,the enhancement of gaseoushydrogen storage dynamics of the samples is believed to be the result of the declined dehydrogenation activation energyresulted from the increase in milling duration and Ni content.
基金the National Natural Science Foundation of China (Grant Nos.51761032, 51471054 and 51871125).
文摘To investigate the influence of adding CeO2 on the hydrogen storage characteristics of Sm-Mg-Ni-based SmMg11Ni-type alloy,mechanical milling was utilized to synthesize SrnMg11Ni and SmMg11Ni +5 wt.%CeO2 (named SmMg11Ni- 5CeO2)alloys.The microstructure of as-castand as-milled samples was measured via X-ray diffractometer and transmission electron microscope.Sieverts device was utilized to measure the isothermal hydriding and dehydriding kinetics. The non-isothermal dehydrogenation performance was explored by thermogravimetry and differential scanning calorimetry.The hydrogen desorption activation energy of the compound metal hydride can be computed by both Arrhenius and Kissinger methods.The related data show that adding CeO2 can engender a very slight influence on the hydrogen storage thermodynamics,but it can result in an obvious reduction in hydrogen absorption and desorption capacities.Furthermore,the hydrogen desorption performance of experimental alloys is conspicuously ameliorated by the addition of CeO2,viz.lowering the initial hydrogen desorption temperature and enhancing hydrogen desorption rate.The hydrogen desorpfion activation energies with and without CeO2 addition are 84.28 and 100.31 kJ/mol,respectively,with an obvious decrease of 16.03 kJ/mol.This is thought to be responsible for the ameliorated hydrogen desorption kinetics by adding CeO2.
