La-Mg-Ni-based hydrogen storage alloys with superlattice structures are the new generation anode material for nickel metal hydride(Ni-MH)batteries owing to the advantages of high capacity and exceptional activation pr...La-Mg-Ni-based hydrogen storage alloys with superlattice structures are the new generation anode material for nickel metal hydride(Ni-MH)batteries owing to the advantages of high capacity and exceptional activation properties.However,the cycling stability is not currently satisfactory enough which plagues its application.Herein,a strategy of partially substituting La with the Y element is proposed to boost the capacity durability of La-Mg-Ni-based alloys.Furthermore,phase structure regulation is implemented simultaneously to obtain the A5 B19-type alloy with good crystal stability specifically.It is found that Y promotes the phase formation of the Pr5 Co19-type phase after annealing at 985℃.The alloy containing Y contributes to the superior rate capability resulting from the promoted hydrogen diffusion rate.Notably,Y substitution enables strengthening the anti-pulverization ability of the alloy in terms of increasing the volume match between[A_(2)B_(4)]and[AB5]subunits,and effectively enhances the anti-corrosion ability of the alloy due to high electronegativity,realizing improved long-term cycling stability of the alloy from 74.2%to 78.5%after cycling 300 times.The work is expected to shed light on the composition and structure design of the La-Mg-Ni-based hydrogen storage alloy for Ni-MH batteries.展开更多
It is well known that in the process of thermal oxidation of silicon,there are P_(b)-type defects at amorphous silicon dioxide/silicon(a-SiO_(2)/Si)interface due to strain.These defects have a very important impact on...It is well known that in the process of thermal oxidation of silicon,there are P_(b)-type defects at amorphous silicon dioxide/silicon(a-SiO_(2)/Si)interface due to strain.These defects have a very important impact on the performance and reliability of semiconductor devices.In the process of passivation,hydrogen is usually used to inactivate P_(b)-type defects by the reaction P_(b)+H_(2)→P_(b)H+H.At the same time,P_(b)H centers dissociate according to the chemical reaction P_(b)H→P_(b)+H.Therefore,it is of great significance to study the balance of the passivation and dissociation.In this work,the reaction mechanisms of passivation and dissociation of the P_(b)-type defects are investigated by first-principles calculations.The reaction rates of the passivation and dissociation are calculated by the climbing image-nudged elastic band(CI-NEB)method and harmonic transition state theory(HTST).By coupling the rate equations of the passivation and dissociation reactions,the equilibrium density ratio of the saturated interfacial dangling bonds and interfacial defects(P_(b),P_(b)0,and P_(b)1)at different temperatures is calculated.展开更多
In order to ameliorate the electrochemical hydrogen storage performance of La-Mg-Ni system A2B7-type electrode alloys, a small amount of Si was added. The La0.8Mg0.2Ni3.3Co0.2Six （x=0-0.2） electrode alloys were prep...In order to ameliorate the electrochemical hydrogen storage performance of La-Mg-Ni system A2B7-type electrode alloys, a small amount of Si was added. The La0.8Mg0.2Ni3.3Co0.2Six （x=0-0.2） electrode alloys were prepared by casting and annealing. The effects of adding Si on the structure and electrochemical hydrogen storage characteristics of the alloys were investigated systematically. The results indicate that the as-cast and annealed alloys hold multiple structures, involving two major phases of （La, Mg）2Ni7 with a Ce2Ni7-type hexagonal structure and LaNi5 with a CaCu5-type hexagonal structure as well as one residual phase LaNi3. The addition of Si results in a decrease in （La, Mg）2Ni7 phase and an increase in LaNi5 phase without changing the phase structure of the alloys. What is more, it brings on an obvious effect on electrochemical hydrogen storage characteristics of the alloys. The discharge capacities of the as-cast and annealed alloys decline with the increase of Si content, but their cycle stabilities clearly grow under the same condition. Furthermore, the measurements of the high rate discharge ability, the limiting current density, hydrogen diffusion coefficient as well as electrochemical impedance spectra all indicate that the electrochemical kinetic properties of the electrode alloys first increase and then decrease with the rising of Si content.展开更多
In order to improve the electrochemical cycle stability of the RE–Mg–Ni-based A2B7-type electrode alloys, a small amount of Si has been added into the alloys.The casting and annealing technologies were adopted to fa...In order to improve the electrochemical cycle stability of the RE–Mg–Ni-based A2B7-type electrode alloys, a small amount of Si has been added into the alloys.The casting and annealing technologies were adopted to fabricate the La0.8Mg0.2Ni3.3Co0.2Six(x = 0–0.2) electrode alloys. The impacts of the addition of Si and annealing treatment on the structures and electrochemical performances of the alloys were investigated systematically. The results obtained by XRD and SEM show that all the as-cast and annealed alloys are of a multiphase structure, involving two main phases(La, Mg)2Ni7and La Ni5 as well as a residual phase La Ni3. Both adding Si and the annealing treatment lead to an evident change in the phase abundance and cell parameters of(La, Mg)2Ni7and La Ni5 major phases of the alloy without altering its main phase component. Moreover, the annealing treatment has the composition of the alloy distributed more homogeneously overall and simultaneously causes the grain of the alloy to be coarsened obviously. The electrochemical measurements indicate that adding Si and the annealing treatment give a significant rise to the influence on the electrochemical performances of the alloys. In brief, the cycle stability of the as-cast and annealed alloys evidently increases with the rising of Si content, while their discharge capacities obviously decrease under the same circumstances. Furthermore, the electrochemical kineticproperties of the electrode alloys, including the high rate discharge ability, the limiting current density(IL), hydrogen diffusion coefficient(D), and the charge-transfer resistance, first augment and then decline with the rising of Si content. Similarly, it is found that the above-mentioned electrochemical properties first mount up and then go down with the rising annealing temperature.展开更多
The casting and annealing technologies were applied to fabricate the La0.8Mg0.2Ni3.3Co0.2Six （x = 0-0.2） electrode alloys. The effects of Si content and annealing temperature on the structure and electrochemical per...The casting and annealing technologies were applied to fabricate the La0.8Mg0.2Ni3.3Co0.2Six （x = 0-0.2） electrode alloys. The effects of Si content and annealing temperature on the structure and electrochemical performances of the alloys were investigated systematically. The analyses of XRD and SEM show that all the alloys possess a multiphase structure, involving two main phases （La, Mg）2Ni7 and LaNi5 as well as a residual phase LaNi3. The addition of Si brings on an evident increase in the LaNi5 phase and a decrease in the （La, Mg）2Ni7 phase, without altering the main phase component of the alloy, which also makes the lattice constants and cell volumes of the alloy enlarged. Likewise, the annealing treatment engenders the same action on the lattice constants and cell volumes as adding Si. Simultaneously, it gives rise to the variation of the phase abundance and the coarsening of the alloy grains. The electrochemical measurements indicate that the addition of Si ameliorates the cycle stability of the as-cast and annealed alloys significantly, but impairs their discharge capacities clearly. Similarly, the annealing treatment makes a positive contribution to the cycle stability of the alloy evidently, and the discharge capacity of the alloy shows a maximum value with annealing temperature rising. Furthermore, the high rate discharge ability （HR） first augments and then declines with the rising of Si content and annealing temperature.展开更多
Investigation of alloy structure shows that La2-xMgxNi7 （x = 0.3 - 0.8） alloys are mainly com- posed of Ce/Ni7-type, Gd2Co7-type and PuNi3-type phase. The influence of Mg content in alloys on the phase structure is ...Investigation of alloy structure shows that La2-xMgxNi7 （x = 0.3 - 0.8） alloys are mainly com- posed of Ce/Ni7-type, Gd2Co7-type and PuNi3-type phase. The influence of Mg content in alloys on the phase structure is great, resulting in a linear decrease of the unit cell parameters of main phases and increase of hydrogen absorption/desorption plateau as Mg content increases. Electrochemical measurements show that as the Mg content increases, the discharge capacity of alloy electrodes first increases and then decreases. The cyclic stability presents a deteriorative trend. La1.4Mg0.6 Ni7 alloy electrode exhibits the maximum electrochemical discharge capacity （378 mAh·g^-1）, and the La1.6Mg0.4Ni7 alloy electrode shows the best cyclic stability （S270 = 81%）.展开更多
A series of hydrogen storage Co-free AB3-type alloys were directly synthesized with vacuum mid-frequency melting method,within which Ni of La0.7Mg0.3Ni3 alloy was substituted by Fe,B and(FeB) alloy,respectively.Alloys...A series of hydrogen storage Co-free AB3-type alloys were directly synthesized with vacuum mid-frequency melting method,within which Ni of La0.7Mg0.3Ni3 alloy was substituted by Fe,B and(FeB) alloy,respectively.Alloys were characterized by XRD,EDS and SEM to investigate the effects of B and Fe substitution for Ni on material structure.The content of LaMg2Ni9 phase within La0.7Mg0.3Ni3 alloy reaches 37.9% and that of La0.7Mg0.3Ni2.9(FeB)0.1 alloys reduces to 23.58%.Among all samples,ground particles with different shapes correspond to different phases.The major substitution occurs in LaMg2Ni9 phase.Electrochemical tests indicate that substituted alloys have different electrochemical performance,which is affected by phase structures of alloy.The discharge capacity of La0.7Mg0.3Ni3 alloy reaches 337.3 mA·h/g,but La0.7Mg0.3Ni2.9(FeB)0.1 alloy gets better high rate discharge(HRD) performance at the discharge rate of 500 mA/g with a high HRD value of 73.19%.展开更多
The growing dema nds of supramolecular hyperbranched polymers integrati ng non covale nt in teraction and unique topological structure merits had received considerable interest in the fabrication of novel materials fo...The growing dema nds of supramolecular hyperbranched polymers integrati ng non covale nt in teraction and unique topological structure merits had received considerable interest in the fabrication of novel materials for advaneed applications.Herein,we prepared A2B6-type POSS-containing supramolecular hyperbranched polymers with multiple morphologies including lamellar-like,branched,hollow,core-shell and porous spherical structures through regulating self-assembling monomer concentrations and solvent polarities.The incorporation of appropriate emulative vip molecules would further trigger morphological transformations(such as vesicles and spherical micelles)by synergistic effects of unique POSS aggregation ability,supramolecular complexations and hydrophilic-hydrophobic interactions.Thus,this facile and universal strategy may enable a modular nanofabrication of supramolecular hyperbranched polymers with diversiform topological structure and sophisticated multifunctionality for their potential applications.展开更多
The partial substitution of Zr for La has been performed in order to ameliorate the electrochemical hydrogen storage performances of La–Mg–Ni based A2B7-type electrode alloys. The melt spinning technology was used t...The partial substitution of Zr for La has been performed in order to ameliorate the electrochemical hydrogen storage performances of La–Mg–Ni based A2B7-type electrode alloys. The melt spinning technology was used to prepare the La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1 (x=0, 0.05, 0.1, 0.15, 0.2) electrode alloys. The impacts of the melt spinning and the substituting La with Zr on the structures and the electrochemical hydrogen storage characteristics of the alloys were systemically investigated. The analysis of XRD and TEM 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 electrochemical measurement indicates that both the substitution of Zr for La and the melt spinning ameliorate the electrochemical cycle stability of the alloys dramatically. Furthermore, the high rate discharge ability (HRD) of the as-spun (10 m/s) alloys notably declines with growing the amount of Zr substitution, while it first augments and then falls for the (x=0.1) alloy with rising the spinning rate.展开更多
The La-Mg-Ni-based A2B7-type Lao.8_xNdx Mgo.2Ni3.35Alo.lSio.o5 （x = 0, 0.1, 0.2, 0.3, and 0.4） electrode alloys were prepared by casting and annealing. The influence of the partial substitution of Nd for La on the s...The La-Mg-Ni-based A2B7-type Lao.8_xNdx Mgo.2Ni3.35Alo.lSio.o5 （x = 0, 0.1, 0.2, 0.3, and 0.4） electrode alloys were prepared by casting and annealing. The influence of the partial substitution of Nd for La on the structure and electrochemical performances of the alloys was investigated. The structural analysis of X-ray diffraction and scanning electron microscopy reveals that the experimental alloys consist of two major phases： （La,Mg）2Ni7 with the hexagonal Ce2Ni7-type structure and LaNi5 with the hexagonal CaCus-type structure as well as some residual phases of LaNi3 and NdNis. The electrochemical measurements indicate that an evident change of the electrochemical performance of the alloys is associated with the substitution of Nd for La. The discharge capacity of the alloy first increases then decreases with the growing Nd content, whereas their cycle stability clearly grows all the time. Furthermore, the measurements of the high rate discharge ability, the limiting current density, and hydrogen diffusion coefficient all demonstrate that the electrochemical kinetic properties of the alloy electrodes first augment then decline with the rising amount of Nd substitution.展开更多
The La-Mg-Ni-based A2B7-type La0.5Mg0.2Ni3.3Co0.2Six （x=0-0.2） electrode alloys were prepared by casting and annealing. The influences of the additional silicon and the annealing treatment on the structure and elect...The La-Mg-Ni-based A2B7-type La0.5Mg0.2Ni3.3Co0.2Six （x=0-0.2） electrode alloys were prepared by casting and annealing. The influences of the additional silicon and the annealing treatment on the structure and electrochemical performances of the alloys were investigated systemically. Both of the analyses of XRD and SEM reveal that the as-cast and annealed alloys are of a multiphase structure, involving two main phases （La, Mg）2Ni7 and LaNi5 as well as one minor phase LaNi3. The addition of Si and annealing treatment bring on an evident change in the phase abundances and cell parameters of （La, Mg）2Ni7 and LaNi5 phase for the alloy without altering its phase structure. The phase abundances decrease from 74.3% （x=0） to 57.8% （x=0.2） for the （La, Mg）2Ni7 phase, and those of LaNi5 phase increase from 20.2% （x^0） to 37.3% （x=0.2）. As for the electrochemical measurements, adding Si and performing annealing treatment have engendered obvious impacts. The cycle stability of the alloys is improved dramatically, being enhanced from 80.3% to 93.7% for the as-annealed （950 ℃） alloys with Si content increasing from 0 to 0.2. However, the discharge capacity is reduced by adding Si, from 399.4 to 345.3 mA.h/g as the Si content increases from 0 to 0.2. Furthermore, such addition makes the electrochemical kinetic properties of the alloy electrodes first increase and then decrease. Also, it is found that the overall electrochemical properties of the alloys first augment and then fall with the annealing temperature rising.展开更多
The La-Mg-Ni system A2B7-type electrode alloys with nominal composition La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1(x=0,0.05, 0.1,0.15,0.2)were prepared by casting and melt-spinning.The influences of melt spinning on the electro...The La-Mg-Ni system A2B7-type electrode alloys with nominal composition La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1(x=0,0.05, 0.1,0.15,0.2)were prepared by casting and melt-spinning.The influences of melt spinning on the electrochemical performances as well as the structures of the alloys were investigated.The results obtained by XRD,SEM and TEM show that the as-cast and spun alloys have a multiphase structure,consisting of two main phases(La,Mg)Ni3 and LaNi5 as well as a residual phase LaNi2.The melt spinning leads to an obvious increase of the LaNi5 phase and a decrease of the(La,Mg)Ni3 phase in the alloys.The results of the electrochemical measurement indicate that the discharge capacity of the alloys(x≤0.1)first increases and then decreases with the increase of spinning rate,whereas for x>0.1,the discharge capacity of the alloys monotonously falls.The melt spinning slightly impairs the activation capability of the alloys,but it significantly enhances the cycle stability of the alloys.展开更多
The work is mainly to study the thermal stability including the phase stability, microstructure and tribo-mechanical properties of the AlB_2-type WB_2 and W–B–N(5.6 at.% N) films annealed in vacuum at various temper...The work is mainly to study the thermal stability including the phase stability, microstructure and tribo-mechanical properties of the AlB_2-type WB_2 and W–B–N(5.6 at.% N) films annealed in vacuum at various temperatures, which are deposited on Si and GY8 substrates by magnetron sputtering. For the WB_2 and W–B–N films deposited on Si wafers, as the annealing temperature increases from 700 to 1000 °C, a-WB(700 °C) and Mo_2B_5-type WB_2(1000 °C) are successively observed in the AlB_2-type WB_2 films, which show many cracks at the temperature ≥ 800 °C resulting in the performance failure; by contrast, only slight α-WB is observed at 1000 °C in the W–B–N films due to the stabilization eff ect of a-BN phase, and the hardness increases to 34.1 GPa fi rst due to the improved crystallinity and then decreases to 31.5 GPa ascribed to the formation of α-WB. For the WB_2 and the W–B–N films deposited on WC–Co substrates, both the WB_2 and W–B–N films react with the YG8(WC–Co) substrates leading to the formation of CoWB, CoW_2B_2 and CoW_3B_3 with the annealing temperature increasing to 900 °C; a large number of linear cracks occur on the surface of these two films annealed at ≥ 800 °C leading to the fi lm failure; after vacuum annealing at 700 °C, the friction performance of the W–B–N films is higher than that of the deposited W–B–N films, while the wear resistance of the WB_2 films shows a slight decrease compared with that of the deposited WB_2 films.展开更多
The La-Mg-Ni-based A2B7-type La0.8-xNdxMg0.2Ni3.15Co0.2Al0.15 （x=0, 0.1, 0.2, 0.3, 0.4） electrode alloys were prepared by casting and annealing. The influences of partial substitution of Nd for La on the structure a...The La-Mg-Ni-based A2B7-type La0.8-xNdxMg0.2Ni3.15Co0.2Al0.15 （x=0, 0.1, 0.2, 0.3, 0.4） electrode alloys were prepared by casting and annealing. The influences of partial substitution of Nd for La on the structure and electrochemical performance of the as-cast and annealed alloys were investigated. It was found that the experimental alloys consist of two major phases, （La, Mg）2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure, as well as some residual phase LaNi3 and NdNi5. The discharge capacity and high rate discharge ability （HRD） of the as-cast and annealed alloys first increase and then decrease with Nd content growing. The as-cast and annealed alloys （x=0.3） yield the largest discharge capacities of 380.3 and 384.3 mA·h/g, respectively. The electrochemical cycle stability of the as-cast and annealed alloys markedly grows with Nd content rising. As the Nd content increase from 0 to 0.4. The capacity retaining rate （S100） at the 100th charging and discharging cycle increases from 64.98% to 85.17% for the as-cast alloy, and from 76.60% to 96.84% for the as-annealed alloy.展开更多
To improve the cyclic stability of La-Mg-Ni system alloy, as-cast La0.75Mg0.25Ni3.5Co0.2 alloy was annealed at 1123, 1223, and 1323 K for 10 h in 0.3 MPa argon. The microstructure and electrochemical performance of di...To improve the cyclic stability of La-Mg-Ni system alloy, as-cast La0.75Mg0.25Ni3.5Co0.2 alloy was annealed at 1123, 1223, and 1323 K for 10 h in 0.3 MPa argon. The microstructure and electrochemical performance of different annealed alloys were investigated systematically by X-Ray Diffraction （XRD）, Scanning Electron Microscopy （SEM）, X-Ray Photoelectron Spectroscopy （XPS）, and electrochemical experiments. The results obtained by XRD and SEM showed that the as-cast and annealed （1123 K） alloys had multiphase structure containing LaNis, （La, Mg）2（Ni, Co）7 and few LaNi2 phases. When annealing temperatures approached 1223 and 1323 K, LaNi2 phase disappeared. The annealed alloys at 1223 and 1323 K were composed of LaNi5, （La, Mg）2（Ni, Co）7 and （La, Mg）（Ni, Co）3 phases. With increasing annealing temperature, the maximum discharge capacity of the alloy decreased monotonously, but the cyclic stability was improved owing to structure homogeneity and grain growth after annealing, as well as the enhancement of anti-oxidation/corrosion ability and the suppression of pulverization during cycling in KOH electrolyte.展开更多
In order to ameliorate the electrochemical cycle stability of the RE-Mg-Ni based A2B7-type electrode alloys, the Mg content in the alloy was reduced and La in the alloy was partially substituted by Sm. The La0.8-xSmxM...In order to ameliorate the electrochemical cycle stability of the RE-Mg-Ni based A2B7-type electrode alloys, the Mg content in the alloy was reduced and La in the alloy was partially substituted by Sm. The La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 （x=0, 0.1, 0.2, 0.3, 0.4） elec-trode alloys were fabricated by casting and annealing. The microstructures of the as-cast and annealed alloys were characterized by XRD and SEM. The electrochemical hydrogen storage characteristics of the as-cast and annealed alloys were measured. The results revealed that all of the experimental alloys mainly consisted of two phases： （La,Mg）2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure. As Sm content grew from 0 to 0.4, the discharge capacity and the high rate discharge ability （HRD） first in-creased and then decreased for the as-cast and annealed alloys, whereas the capacity retaining rate （S100） after 100 cycles increased continuously.展开更多
基金the financial support by the National Nat-ural Science Foundation of China(Nos.52201282,52071281,52371239)the China Postdoctoral Science Foundation(No.2023M742945)+4 种基金Hebei Provincial Postdoctoral Science Foundation(No.B2023003023)the Science Research Project of Hebei Education Department(No.BJK2022033)the Natural Science Foundation of Hebei Province(No.C2022203003)the Inner Mongolia Science and Technology Major Project(No.2020ZD0012)the Baotou Science and Technology Planning Project(No.XM2022BT09).
文摘La-Mg-Ni-based hydrogen storage alloys with superlattice structures are the new generation anode material for nickel metal hydride(Ni-MH)batteries owing to the advantages of high capacity and exceptional activation properties.However,the cycling stability is not currently satisfactory enough which plagues its application.Herein,a strategy of partially substituting La with the Y element is proposed to boost the capacity durability of La-Mg-Ni-based alloys.Furthermore,phase structure regulation is implemented simultaneously to obtain the A5 B19-type alloy with good crystal stability specifically.It is found that Y promotes the phase formation of the Pr5 Co19-type phase after annealing at 985℃.The alloy containing Y contributes to the superior rate capability resulting from the promoted hydrogen diffusion rate.Notably,Y substitution enables strengthening the anti-pulverization ability of the alloy in terms of increasing the volume match between[A_(2)B_(4)]and[AB5]subunits,and effectively enhances the anti-corrosion ability of the alloy due to high electronegativity,realizing improved long-term cycling stability of the alloy from 74.2%to 78.5%after cycling 300 times.The work is expected to shed light on the composition and structure design of the La-Mg-Ni-based hydrogen storage alloy for Ni-MH batteries.
基金Project supported by the Science Challenge Project,China(Grant No.TZ2016003-1-105)the Tianjin Natural Science Foundation,China(Grant No.20JCZDJC00750)the Fundamental Research Funds for the Central Universities,Nankai University(Grant Nos.63211107 and 63201182).
文摘It is well known that in the process of thermal oxidation of silicon,there are P_(b)-type defects at amorphous silicon dioxide/silicon(a-SiO_(2)/Si)interface due to strain.These defects have a very important impact on the performance and reliability of semiconductor devices.In the process of passivation,hydrogen is usually used to inactivate P_(b)-type defects by the reaction P_(b)+H_(2)→P_(b)H+H.At the same time,P_(b)H centers dissociate according to the chemical reaction P_(b)H→P_(b)+H.Therefore,it is of great significance to study the balance of the passivation and dissociation.In this work,the reaction mechanisms of passivation and dissociation of the P_(b)-type defects are investigated by first-principles calculations.The reaction rates of the passivation and dissociation are calculated by the climbing image-nudged elastic band(CI-NEB)method and harmonic transition state theory(HTST).By coupling the rate equations of the passivation and dissociation reactions,the equilibrium density ratio of the saturated interfacial dangling bonds and interfacial defects(P_(b),P_(b)0,and P_(b)1)at different temperatures is calculated.
基金Projects(50961009,51161015)supported by the National Natural Science Foundation of ChinaProject(2011AA03A408)supported by the High-tech Research and Development Program of ChinaProjects(2011ZD10,2010ZD05)supported by the Natural Science Foundation of Inner Mongolia,China
文摘In order to ameliorate the electrochemical hydrogen storage performance of La-Mg-Ni system A2B7-type electrode alloys, a small amount of Si was added. The La0.8Mg0.2Ni3.3Co0.2Six （x=0-0.2） electrode alloys were prepared by casting and annealing. The effects of adding Si on the structure and electrochemical hydrogen storage characteristics of the alloys were investigated systematically. The results indicate that the as-cast and annealed alloys hold multiple structures, involving two major phases of （La, Mg）2Ni7 with a Ce2Ni7-type hexagonal structure and LaNi5 with a CaCu5-type hexagonal structure as well as one residual phase LaNi3. The addition of Si results in a decrease in （La, Mg）2Ni7 phase and an increase in LaNi5 phase without changing the phase structure of the alloys. What is more, it brings on an obvious effect on electrochemical hydrogen storage characteristics of the alloys. The discharge capacities of the as-cast and annealed alloys decline with the increase of Si content, but their cycle stabilities clearly grow under the same condition. Furthermore, the measurements of the high rate discharge ability, the limiting current density, hydrogen diffusion coefficient as well as electrochemical impedance spectra all indicate that the electrochemical kinetic properties of the electrode alloys first increase and then decrease with the rising of Si content.
基金financially supported by the National Natural Science Foundation of China (Nos. 50961009 and 51161015)the National High Technology Research and Development Program of China (No. 2011AA03A408)the National High Technology Research and Development Program of China (Nos. 2011ZD10 and 2010ZD05)
文摘In order to improve the electrochemical cycle stability of the RE–Mg–Ni-based A2B7-type electrode alloys, a small amount of Si has been added into the alloys.The casting and annealing technologies were adopted to fabricate the La0.8Mg0.2Ni3.3Co0.2Six(x = 0–0.2) electrode alloys. The impacts of the addition of Si and annealing treatment on the structures and electrochemical performances of the alloys were investigated systematically. The results obtained by XRD and SEM show that all the as-cast and annealed alloys are of a multiphase structure, involving two main phases(La, Mg)2Ni7and La Ni5 as well as a residual phase La Ni3. Both adding Si and the annealing treatment lead to an evident change in the phase abundance and cell parameters of(La, Mg)2Ni7and La Ni5 major phases of the alloy without altering its main phase component. Moreover, the annealing treatment has the composition of the alloy distributed more homogeneously overall and simultaneously causes the grain of the alloy to be coarsened obviously. The electrochemical measurements indicate that adding Si and the annealing treatment give a significant rise to the influence on the electrochemical performances of the alloys. In brief, the cycle stability of the as-cast and annealed alloys evidently increases with the rising of Si content, while their discharge capacities obviously decrease under the same circumstances. Furthermore, the electrochemical kineticproperties of the electrode alloys, including the high rate discharge ability, the limiting current density(IL), hydrogen diffusion coefficient(D), and the charge-transfer resistance, first augment and then decline with the rising of Si content. Similarly, it is found that the above-mentioned electrochemical properties first mount up and then go down with the rising annealing temperature.
基金Funded by National Natural Science Foundations of China(Nos.51161015 and 51371094)National 863 Plans Projects of China(No.2011AA03A408)
文摘The casting and annealing technologies were applied to fabricate the La0.8Mg0.2Ni3.3Co0.2Six （x = 0-0.2） electrode alloys. The effects of Si content and annealing temperature on the structure and electrochemical performances of the alloys were investigated systematically. The analyses of XRD and SEM show that all the alloys possess a multiphase structure, involving two main phases （La, Mg）2Ni7 and LaNi5 as well as a residual phase LaNi3. The addition of Si brings on an evident increase in the LaNi5 phase and a decrease in the （La, Mg）2Ni7 phase, without altering the main phase component of the alloy, which also makes the lattice constants and cell volumes of the alloy enlarged. Likewise, the annealing treatment engenders the same action on the lattice constants and cell volumes as adding Si. Simultaneously, it gives rise to the variation of the phase abundance and the coarsening of the alloy grains. The electrochemical measurements indicate that the addition of Si ameliorates the cycle stability of the as-cast and annealed alloys significantly, but impairs their discharge capacities clearly. Similarly, the annealing treatment makes a positive contribution to the cycle stability of the alloy evidently, and the discharge capacity of the alloy shows a maximum value with annealing temperature rising. Furthermore, the high rate discharge ability （HR） first augments and then declines with the rising of Si content and annealing temperature.
文摘Investigation of alloy structure shows that La2-xMgxNi7 （x = 0.3 - 0.8） alloys are mainly com- posed of Ce/Ni7-type, Gd2Co7-type and PuNi3-type phase. The influence of Mg content in alloys on the phase structure is great, resulting in a linear decrease of the unit cell parameters of main phases and increase of hydrogen absorption/desorption plateau as Mg content increases. Electrochemical measurements show that as the Mg content increases, the discharge capacity of alloy electrodes first increases and then decreases. The cyclic stability presents a deteriorative trend. La1.4Mg0.6 Ni7 alloy electrode exhibits the maximum electrochemical discharge capacity （378 mAh·g^-1）, and the La1.6Mg0.4Ni7 alloy electrode shows the best cyclic stability （S270 = 81%）.
基金Project(2007AA11A104) supported by the High-tech Research and Development Program of ChinaProject(2009CB220100) supported by the National Basic Research Program of China
文摘A series of hydrogen storage Co-free AB3-type alloys were directly synthesized with vacuum mid-frequency melting method,within which Ni of La0.7Mg0.3Ni3 alloy was substituted by Fe,B and(FeB) alloy,respectively.Alloys were characterized by XRD,EDS and SEM to investigate the effects of B and Fe substitution for Ni on material structure.The content of LaMg2Ni9 phase within La0.7Mg0.3Ni3 alloy reaches 37.9% and that of La0.7Mg0.3Ni2.9(FeB)0.1 alloys reduces to 23.58%.Among all samples,ground particles with different shapes correspond to different phases.The major substitution occurs in LaMg2Ni9 phase.Electrochemical tests indicate that substituted alloys have different electrochemical performance,which is affected by phase structures of alloy.The discharge capacity of La0.7Mg0.3Ni3 alloy reaches 337.3 mA·h/g,but La0.7Mg0.3Ni2.9(FeB)0.1 alloy gets better high rate discharge(HRD) performance at the discharge rate of 500 mA/g with a high HRD value of 73.19%.
基金by the Ministry of Science and Technology of China(No.2020YFA0908900)the National Natural Science Foundation of China(Nos.51973226,21935011,21725403 and 81871782)the Youth Innovation Promotion Association CAS(No.2019031).
文摘The growing dema nds of supramolecular hyperbranched polymers integrati ng non covale nt in teraction and unique topological structure merits had received considerable interest in the fabrication of novel materials for advaneed applications.Herein,we prepared A2B6-type POSS-containing supramolecular hyperbranched polymers with multiple morphologies including lamellar-like,branched,hollow,core-shell and porous spherical structures through regulating self-assembling monomer concentrations and solvent polarities.The incorporation of appropriate emulative vip molecules would further trigger morphological transformations(such as vesicles and spherical micelles)by synergistic effects of unique POSS aggregation ability,supramolecular complexations and hydrophilic-hydrophobic interactions.Thus,this facile and universal strategy may enable a modular nanofabrication of supramolecular hyperbranched polymers with diversiform topological structure and sophisticated multifunctionality for their potential applications.
文摘The partial substitution of Zr for La has been performed in order to ameliorate the electrochemical hydrogen storage performances of La–Mg–Ni based A2B7-type electrode alloys. The melt spinning technology was used to prepare the La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1 (x=0, 0.05, 0.1, 0.15, 0.2) electrode alloys. The impacts of the melt spinning and the substituting La with Zr on the structures and the electrochemical hydrogen storage characteristics of the alloys were systemically investigated. The analysis of XRD and TEM 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 electrochemical measurement indicates that both the substitution of Zr for La and the melt spinning ameliorate the electrochemical cycle stability of the alloys dramatically. Furthermore, the high rate discharge ability (HRD) of the as-spun (10 m/s) alloys notably declines with growing the amount of Zr substitution, while it first augments and then falls for the (x=0.1) alloy with rising the spinning rate.
基金supported by the National Natural Science Foundation of China(Nos.51161015 and 50961009)the National High Technology Research and Development Program of China(No.2011AA03A408)the Natural Science Foundation of Inner Mongolia(Nos.2011ZD10 and 2010ZD05)
文摘The La-Mg-Ni-based A2B7-type Lao.8_xNdx Mgo.2Ni3.35Alo.lSio.o5 （x = 0, 0.1, 0.2, 0.3, and 0.4） electrode alloys were prepared by casting and annealing. The influence of the partial substitution of Nd for La on the structure and electrochemical performances of the alloys was investigated. The structural analysis of X-ray diffraction and scanning electron microscopy reveals that the experimental alloys consist of two major phases： （La,Mg）2Ni7 with the hexagonal Ce2Ni7-type structure and LaNi5 with the hexagonal CaCus-type structure as well as some residual phases of LaNi3 and NdNis. The electrochemical measurements indicate that an evident change of the electrochemical performance of the alloys is associated with the substitution of Nd for La. The discharge capacity of the alloy first increases then decreases with the growing Nd content, whereas their cycle stability clearly grows all the time. Furthermore, the measurements of the high rate discharge ability, the limiting current density, and hydrogen diffusion coefficient all demonstrate that the electrochemical kinetic properties of the alloy electrodes first augment then decline with the rising amount of Nd substitution.
基金Projects(51371094,51161015)supported by the National Natural Science Foundations of ChinaProject(2011ZD10)supported by Natural Science Foundation of Inner Mongolia,China
文摘The La-Mg-Ni-based A2B7-type La0.5Mg0.2Ni3.3Co0.2Six （x=0-0.2） electrode alloys were prepared by casting and annealing. The influences of the additional silicon and the annealing treatment on the structure and electrochemical performances of the alloys were investigated systemically. Both of the analyses of XRD and SEM reveal that the as-cast and annealed alloys are of a multiphase structure, involving two main phases （La, Mg）2Ni7 and LaNi5 as well as one minor phase LaNi3. The addition of Si and annealing treatment bring on an evident change in the phase abundances and cell parameters of （La, Mg）2Ni7 and LaNi5 phase for the alloy without altering its phase structure. The phase abundances decrease from 74.3% （x=0） to 57.8% （x=0.2） for the （La, Mg）2Ni7 phase, and those of LaNi5 phase increase from 20.2% （x^0） to 37.3% （x=0.2）. As for the electrochemical measurements, adding Si and performing annealing treatment have engendered obvious impacts. The cycle stability of the alloys is improved dramatically, being enhanced from 80.3% to 93.7% for the as-annealed （950 ℃） alloys with Si content increasing from 0 to 0.2. However, the discharge capacity is reduced by adding Si, from 399.4 to 345.3 mA.h/g as the Si content increases from 0 to 0.2. Furthermore, such addition makes the electrochemical kinetic properties of the alloy electrodes first increase and then decrease. Also, it is found that the overall electrochemical properties of the alloys first augment and then fall with the annealing temperature rising.
基金Project(2007AA03Z227)supported by High-tech Research and Development Program of ChinaProjects(50871050,50701011)supported by the National Natural Science Foundation of China+1 种基金Project(200711020703)supported by the Natural Science Foundation of Inner Mongolia,ChinaProject(NJzy08071)supported by High Education Science Research Project of Inner Mongolia,China
文摘The La-Mg-Ni system A2B7-type electrode alloys with nominal composition La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1(x=0,0.05, 0.1,0.15,0.2)were prepared by casting and melt-spinning.The influences of melt spinning on the electrochemical performances as well as the structures of the alloys were investigated.The results obtained by XRD,SEM and TEM show that the as-cast and spun alloys have a multiphase structure,consisting of two main phases(La,Mg)Ni3 and LaNi5 as well as a residual phase LaNi2.The melt spinning leads to an obvious increase of the LaNi5 phase and a decrease of the(La,Mg)Ni3 phase in the alloys.The results of the electrochemical measurement indicate that the discharge capacity of the alloys(x≤0.1)first increases and then decreases with the increase of spinning rate,whereas for x>0.1,the discharge capacity of the alloys monotonously falls.The melt spinning slightly impairs the activation capability of the alloys,but it significantly enhances the cycle stability of the alloys.
基金supported by the National Natural Science Foundation of China (Nos. 51701157 and 51505378)the Natural Science Foundation of Shaanxi Province of China (No. 2017JQ5031)
文摘The work is mainly to study the thermal stability including the phase stability, microstructure and tribo-mechanical properties of the AlB_2-type WB_2 and W–B–N(5.6 at.% N) films annealed in vacuum at various temperatures, which are deposited on Si and GY8 substrates by magnetron sputtering. For the WB_2 and W–B–N films deposited on Si wafers, as the annealing temperature increases from 700 to 1000 °C, a-WB(700 °C) and Mo_2B_5-type WB_2(1000 °C) are successively observed in the AlB_2-type WB_2 films, which show many cracks at the temperature ≥ 800 °C resulting in the performance failure; by contrast, only slight α-WB is observed at 1000 °C in the W–B–N films due to the stabilization eff ect of a-BN phase, and the hardness increases to 34.1 GPa fi rst due to the improved crystallinity and then decreases to 31.5 GPa ascribed to the formation of α-WB. For the WB_2 and the W–B–N films deposited on WC–Co substrates, both the WB_2 and W–B–N films react with the YG8(WC–Co) substrates leading to the formation of CoWB, CoW_2B_2 and CoW_3B_3 with the annealing temperature increasing to 900 °C; a large number of linear cracks occur on the surface of these two films annealed at ≥ 800 °C leading to the fi lm failure; after vacuum annealing at 700 °C, the friction performance of the W–B–N films is higher than that of the deposited W–B–N films, while the wear resistance of the WB_2 films shows a slight decrease compared with that of the deposited WB_2 films.
基金Projects(51161015,50961009)supported by the National Natural Science Foundations of ChinaProject(2011AA03A408)supported by the National Hi-tech Research and Development Program of ChinaProjects(2011ZD10,2010ZD05)supported by the Natural Science Foundation of Inner Mongolia,China
文摘The La-Mg-Ni-based A2B7-type La0.8-xNdxMg0.2Ni3.15Co0.2Al0.15 （x=0, 0.1, 0.2, 0.3, 0.4） electrode alloys were prepared by casting and annealing. The influences of partial substitution of Nd for La on the structure and electrochemical performance of the as-cast and annealed alloys were investigated. It was found that the experimental alloys consist of two major phases, （La, Mg）2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure, as well as some residual phase LaNi3 and NdNi5. The discharge capacity and high rate discharge ability （HRD） of the as-cast and annealed alloys first increase and then decrease with Nd content growing. The as-cast and annealed alloys （x=0.3） yield the largest discharge capacities of 380.3 and 384.3 mA·h/g, respectively. The electrochemical cycle stability of the as-cast and annealed alloys markedly grows with Nd content rising. As the Nd content increase from 0 to 0.4. The capacity retaining rate （S100） at the 100th charging and discharging cycle increases from 64.98% to 85.17% for the as-cast alloy, and from 76.60% to 96.84% for the as-annealed alloy.
基金Project supported by the National Natural Science Foundation of China(50642033 50701011)+1 种基金Key Technologies R&D Program of Inner Mongolia, China (20050205)Natural Science Foundation of Inner Mongolia, China (200711020703)
文摘To improve the cyclic stability of La-Mg-Ni system alloy, as-cast La0.75Mg0.25Ni3.5Co0.2 alloy was annealed at 1123, 1223, and 1323 K for 10 h in 0.3 MPa argon. The microstructure and electrochemical performance of different annealed alloys were investigated systematically by X-Ray Diffraction （XRD）, Scanning Electron Microscopy （SEM）, X-Ray Photoelectron Spectroscopy （XPS）, and electrochemical experiments. The results obtained by XRD and SEM showed that the as-cast and annealed （1123 K） alloys had multiphase structure containing LaNis, （La, Mg）2（Ni, Co）7 and few LaNi2 phases. When annealing temperatures approached 1223 and 1323 K, LaNi2 phase disappeared. The annealed alloys at 1223 and 1323 K were composed of LaNi5, （La, Mg）2（Ni, Co）7 and （La, Mg）（Ni, Co）3 phases. With increasing annealing temperature, the maximum discharge capacity of the alloy decreased monotonously, but the cyclic stability was improved owing to structure homogeneity and grain growth after annealing, as well as the enhancement of anti-oxidation/corrosion ability and the suppression of pulverization during cycling in KOH electrolyte.
基金Project supported by National Natural Science Foundations of China (51161015 and 50961009)National High Technology Research and Development Program of China (2011AA03A408)Natural Science Foundations of Inner Mongolia,China (2011ZD10 and 2010ZD05)
文摘In order to ameliorate the electrochemical cycle stability of the RE-Mg-Ni based A2B7-type electrode alloys, the Mg content in the alloy was reduced and La in the alloy was partially substituted by Sm. The La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 （x=0, 0.1, 0.2, 0.3, 0.4） elec-trode alloys were fabricated by casting and annealing. The microstructures of the as-cast and annealed alloys were characterized by XRD and SEM. The electrochemical hydrogen storage characteristics of the as-cast and annealed alloys were measured. The results revealed that all of the experimental alloys mainly consisted of two phases： （La,Mg）2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure. As Sm content grew from 0 to 0.4, the discharge capacity and the high rate discharge ability （HRD） first in-creased and then decreased for the as-cast and annealed alloys, whereas the capacity retaining rate （S100） after 100 cycles increased continuously.
