The glass-ceramics were prepared with the spodumene mineral as the main raw material,and the effects of ZrO_(2)replacing TiO_(2)on the samples were systematically investigated.The results show that the substitution of...The glass-ceramics were prepared with the spodumene mineral as the main raw material,and the effects of ZrO_(2)replacing TiO_(2)on the samples were systematically investigated.The results show that the substitution of ZrO_(2)for TiO_(2)is not conductive to precipitate𝛽β-quartz solid solution phase,but can improve the transparency and flexural strength of glass-ceramics.And the glass-ceramic with the highest visible light transmittance(87%)and flexural strength(231.80 MPa)exhibits an ultra-low thermal expansion of-0.028×10^(-7)K^(-1)in the region of 30-700℃.展开更多
Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocompo...Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.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
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 La0.8Mg0.2Ni3.3Co0.2Six(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 electroc...The La–Mg–Ni-based A2B7-type La0.8Mg0.2Ni3.3Co0.2Six(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 °C)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 effects of Co as a substituent for Ni on microstructure and electrochemical capacity of hydrogen storage alloys MI(NiCoMnAl)5.4 at -30- +80 ℃, in which the content of Co was 0, 1.31%, 2.63%, 3.94%, 5.25%, and ...The effects of Co as a substituent for Ni on microstructure and electrochemical capacity of hydrogen storage alloys MI(NiCoMnAl)5.4 at -30- +80 ℃, in which the content of Co was 0, 1.31%, 2.63%, 3.94%, 5.25%, and 6.56% (mass fraction), respectively, were reported. All of the alloys were prepared by vacuum induction melting followed by melt-spinning. It is found that the electrochemical capacity of alloys at different temperature depends upon the compositions and preparation methods. The electrochemical capacity of alloys increases at higher temperature (40 - 80 ℃ ) and decreases at lower temperature ( - 30 - 0 ℃ ) with an increasing cobalt content. With an increasing temperature, melt-spinning is more favorable for improved capacity of the alloys than casting. Analyses of the charging/discharging potential curves illustrate that higher cobalt content and melt-spinning techniques are more effective to increase the capacity at higher temperature because of the higher hydrogen evolution potential. On the contrary, the capacity of alloys at lower temperature can be increased by decreasing cobalt content and casting, which is ascribed to higher hydrogen evolution potential and delayed hydrogen evolution reaction, as well as reduced potential drop in the charging/discharging process. XRD patterns confirm that all of the specimens present a single hexagonal CaCu5-type structure and an increased lattice parameters with increasing Co content. The FWHM of the main peak of melt-spun ribbons reduces because of more homogeneous composition and less lattice strain defects.展开更多
In order to improve the cycle stability of La-Mg-Ni-Co type alloy electrode, rapid quenching technology was employed. The effects of rapid quenching on the microstructure and cycle stability of the alloy were investig...In order to improve the cycle stability of La-Mg-Ni-Co type alloy electrode, rapid quenching technology was employed. The effects of rapid quenching on the microstructure and cycle stability of the alloy were investigated. The obtained results show that the La2Mg(Ni0.85Co0.15)9M0.1 (M=B, Cr) alloy electrodes are composed of (La, Mg)Ni3 phase, LaNi5 phase and a small amount of the LaNi2 phase. A trace of the Ni2B phase exists in the as-cast MB alloy, and the Ni2B phase in the alloy nearly disappears after rapid quenching. Rapid quenching technology can slightly improve the cycling life of the alloy. When the quenching rate increases from 0 m·s-1 (As-cast is defined as quenching rate of 0 m·s-1) to 30 m·s-1, the cycle lives of the MB, MCr alloys enhance from 86 and 87 cycles to 106 and 119 cycles, respectively. On the other hand, the average capacity decay rates of the MB, MCr alloys decrease from 1.7172 and 1.7178 mAh·g-1·cycle-1 to 1.5751 and 1.3060 mAh·g-1·cycle-1 after 86 charge-discharges cycling, respectively.展开更多
In order to ameliorate the electrochemical hydrogen storage performances of La-Mg–Ni system A_2B_7-type electrode alloys, the partial substitution of M (M = Zr, Pr) for La was performed. The melt spinning technology ...In order to ameliorate the electrochemical hydrogen storage performances of La-Mg–Ni system A_2B_7-type electrode alloys, the partial substitution of M (M = Zr, Pr) for La was performed. The melt spinning technology was used to fabricate the La_(0.75-x)M_xMg_0.25Ni_3.2Co_0.2Al_0.1 (M = Zr, Pr; x = 0, 0.1) electrode alloys. The influences of the melt spinning and substituting La with M (M = Zr, Pr) on the structures and the electrochemical hydrogen storage characteristics of the alloys were investigated. The analysis of XRD, SEM, and TEM reveals that the as-cast and spun alloys have a multiphase structure composed of two main phases (La, Mg)_2Ni_7 and LaNi_5 as well as a residual phase LaNi_2 . The as-spun (M = Pr) alloy displays an entire nanocrystalline structure, while an amorphous-like structure is detected in the as-spun (M = Zr) alloy, implying that the substitution of Zr for La facilitates the amorphous formation. The electrochemical measurements exhibit that the substitution of Pr for La clearly increases the discharge capacity of the alloys; however, the Zr substitution brings on an adverse impact. Meanwhile, the M (M = Zr, Pr) substitution significantly enhances its cycle stability. The melt spinning exerts an evident effect on the electrochemical performances of the alloys, whose discharge capacity and high rate discharge ability (HRD) first mount up and then fall with the growing spinning rate, whereas their cycle stabilities monotonously augment as the spinning rate increases.展开更多
The Mg2Ni-type alloys with nominal compositions of Mg20Ni10-xCox(x=0,1,2,3,4,%,mass fraction) were prepared by melt-spinning technology.The structures of the alloys were studied by XRD,SEM and HRTEM.The hydrogen absor...The Mg2Ni-type alloys with nominal compositions of Mg20Ni10-xCox(x=0,1,2,3,4,%,mass fraction) were prepared by melt-spinning technology.The structures of the alloys were studied by XRD,SEM and HRTEM.The hydrogen absorption/desorption kinetics and the electrochemical performances of the alloys were measured.The results show that no amorphous phase forms in the as-spun Co-free alloy,but the as-spun alloys containing Co show a certain amount of amorphous phase.The hydrogen absorption capacities of the as-cast alloys first increase and then decrease with the incremental change of Co content.The hydrogen desorption capacities of as-cast and spun alloys rise with increasing Co content.The melt spinning significantly improves the hydrogenation and dehydrogenation capacities and kinetics of the alloys.The substitution of Co for Ni clearly enhances the discharge capacities of the alloys and the cycle stability of the as-spun alloys.展开更多
In order to improve the electrochemical hydrogen storage performance of the Mg2Ni-type electrode alloys, Mg in the alloy was partially substituted by La, and the nanocrystalline and amorphous Mg2Ni-type Mg20-xLaxNi10 ...In order to improve the electrochemical hydrogen storage performance of the Mg2Ni-type electrode alloys, Mg in the alloy was partially substituted by La, and the nanocrystalline and amorphous Mg2Ni-type Mg20-xLaxNi10 (x=0, 2) alloys were synthesized by melt-spinning technique. The microstructures of the as-spun alloys were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical hydrogen storage properties of the experimental alloys were tested. The results show that no amorphous phase is detected in the as-spun Mg20Ni10 alloy, but the as-spun Mg18La2Ni10 alloy holds a major amorphous phase. As La content increases from 0 to 2, the maximum discharge capacity of the as-spun (20 m/s) alloys rises from 96.5 to 387.1 mA·h/g, and the capacity retaining rate (S20) at the 20th cycle grows from 31.3% to 71.7%. Melt-spinning engenders an impactful effect on the electrochemical hydrogen storage performances of the alloys. With the increase in the spinning rate from 0 to 30 m/s, the maximum discharge capacity increases from 30.3 to 135.5 mA·h/g for the Mg20Ni10 alloy, and from 197.2 to 406.5 mA·h/g for the Mg18La2Ni10 alloy. The capacity retaining rate (S20) of the Mg20Ni10 alloy at the 20th cycle slightly falls from 36.7% to 27.1%, but it markedly mounts up from 37.3% to 78.3% for the Mg18La2Ni10 alloy.展开更多
Aiming at the improvement of the cyclic stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloy was partly substituted by Fe. The electrode alloys of La0.7Mg0.3Co0.45Ni255-xFex (x=0, 0.1, ...Aiming at the improvement of the cyclic stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloy was partly substituted by Fe. The electrode alloys of La0.7Mg0.3Co0.45Ni255-xFex (x=0, 0.1, 0.2, 0.3, 0.4) were prepared by casting and rapid quenching. The influence of the quenching on cyclic stability as well as structure of the alloys was investigated in detail. The results of electrochemical measurement indicated that rapid quenching significantly improved cyclic stability. When the quenching rate rose from 0 (As-cast was defined as a quenching rate of 0 m/s) to 30 m/s, the cyclic life of Fe-free alloy (x=-0) increased from 81 to 105 cycles, and for alloy containing Fe(x=0.4), it grew from 106 to 166 cycles at a current density of 600 mA/g. The results obtained by XRD, TEM and SEM revealed that the as-cast and quenched alloys had multiphase structures, including two major phases (La, Mg)Ni3 and LaNi5 as well as an imptLrity phase LaNi2. Rapid quenching helped the formation of an amorphous-like structure in Fe containing alloys.展开更多
For the purpose of improving the electrochemical cycle stability of the La-Mg-Ni based A2B7-type electrode alloys, both reducing Mg content and substituting La with Pr were adopted. The La0.8-xPrxMg0.2Ni3.15Co0.2Al0.1...For the purpose of improving the electrochemical cycle stability of the La-Mg-Ni based A2B7-type electrode alloys, both reducing Mg content and substituting La with Pr were adopted. The La0.8-xPrxMg0.2Ni3.15Co0.2Al0.1Si0.05 (x=0, 0.1, 0.2, 0.3, 0.4) electrode alloys were fabricated by casting and annealing. The investigation on the structures and electrochemical performances of the alloys was performed. The obtained results reveal that the as-cast and annealed alloys comprise two major phases, (La,Mg)2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu 5-type structure, as well as a little residual LaNi3 phase. It is also found that the addition of Pr element observably affects the electrochemical hydrogen storage characteristics of the alloys, just as the discharge capacity and high rate discharge ability (HRD) first rise then fall with the growing of Pr content, and among all the alloys, the as-cast and annealed (x=0.3) alloys generate the largest discharge capacities of 360.8 and 386.5 mA·h/g, respectively. Additionally, the electrochemical cycle stability of all the alloys markedly grows with the increase of Pr content. The capacity retaining rate (S100 ) at the 100th charging and discharging cycle is enhanced from 64.98% to 77.55% for the as-cast alloy, and from 76.60% to 95.72% for the as-annealed alloy by rising Pr content from 0 to 0.4. Furthermore, the substitution of Pr for La results in first increase and then decrease in the hydrogen diffusion coefficient (D), the limiting current density (IL ) as well as the electrochemical impedance.展开更多
In this work,a comprehensive comparison regarding the impacts of M(M=Cu,Co,Mn)substitution for Ni on the structures and the hydrogen storage kinetics of the nanocrystalline and amorphous Mg20Ni10-xMx(M=Cu,Co,Mn; x=0-4...In this work,a comprehensive comparison regarding the impacts of M(M=Cu,Co,Mn)substitution for Ni on the structures and the hydrogen storage kinetics of the nanocrystalline and amorphous Mg20Ni10-xMx(M=Cu,Co,Mn; x=0-4)alloys prepared by melt spinning has been carried out.The analysis of XRD and TEM reveals that the as-spun(M=None,Cu)alloys display an entire nanocrystalline structure,whereas the as-spun(M=Co,Mn)alloys hold a mixed structure of nanocrystalline and amorphous structure when M content x=4,indicating that the substitution of M(M=Co,Mn)for Ni facilitates the glass formation in the Mg2Ni-type alloy.Besides,all the as-spun alloys have a major phase of Mg2Ni but M(M=Co,Mn)substitution brings on the formation of some secondary phases,MgCo2 and Mg phases for M=Co as well as MnNi and Mg phases for M=Mn.Based upon the measurements of the automatic Sieverts apparatus and the automatic galvanostatic system,the impacts engendered by M(M=Cu,Co,Mn)substitution on the gaseous and electrochemical hydrogen storage kinetics of the alloys appear to be evident.The gaseous hydriding kinetics of the alloys first rises and then declines with the growing of M(M=Cu,Co,Mn)content.Particularly,the M(M= Mn)substitution results in a sharp drop in the hydriding kinetics when x=4.The M(M=Cu,Co,Mn)substitution ameliorates the dehydriding kinetics dramatically in the order(M=Co)>(M=Mn)>(M=Cu).The electrochemical kinetics of the alloys visibly grows with M content rising for(M=Cu,Co),while it first increases and then declines for(M=Mn).展开更多
The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD,...The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The alloy electrodes were charged and discharged with a constant current density in order to investigate the electrochemical hydrogen storage kinetics of the alloys. The results demonstrate that the substitution of Co for Ni results in the formation of secondary phases MgCo2 and Mg instead of altering the major phase Mg2Ni. No amorphous phase is detected in the as-quenched Co- ffee alloy, however, a certain amount of amorphous phase is clearly found in the as-quenched alloys substituted by Co. Furthermore, both the rapid quenching and the Co substitution significantly improve the gaseous and electrochemical hydrogen storage kinetics of the alloys, for which the notable increase of the hydrogen diffusion coefficient (D) along with the limiting current density (IL) and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible.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
In order to improve the electrochemical cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloys was partially substituted by M (M=Cu, Al, Mn). A new La-Mg-Ni system electrode alloys La...In order to improve the electrochemical cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloys was partially substituted by M (M=Cu, Al, Mn). A new La-Mg-Ni system electrode alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Cu, Al, Mn; x=0, 0.1) were prepared by casting and rapid quenching. The effects of element substitution and rapid quenching on the microstructures and electrochemical performances of the alloys were investigated. The results by XRD, SEM and TEM show that the alloys have a multiphase structure, including the (La, Mg)Ni3 phase, the LaNi5 phase and the LaNi2 phase. The rapid quenching and element substitution have an imperceptible influence on the phase compositions of the alloys, but both change the phase abundance of the alloys. The rapid quenching significantly improves the composition homogeneity of the alloys and markedly decreases the grain size of the alloys. The Cu substitution promotes the formation of an amorphous phase in the as-quenched alloy, and a reversal result by the Al substitution. The electrochemical measurement indicates that the element substitution decreases the discharge capacity of the alloys, whereas it obviously improves the cycle stability of the alloys. The positive influence of element substitution on the cycle life of the alloys is in sequence Al>Cu>Mn, and negative influence on the discharge capacity is in sequence Al>Mn>Cu. The rapid quenching significantly enhances the cycle stability of the alloys, but it leads to a different extent decrease of the discharge capacity of the alloys.展开更多
In order to improve the cyclic stability of La-Mg-Ni system (Ce2Ni7-type) alloy electrode, small amount of Co was added in La0.75Mg0.25Ni3.5 alloy. The effect of Co on electrochemical performance and microstructure ...In order to improve the cyclic stability of La-Mg-Ni system (Ce2Ni7-type) alloy electrode, small amount of Co was added in La0.75Mg0.25Ni3.5 alloy. The effect of Co on electrochemical performance and microstructure of the alloys were investigated in detail. XRD results showed that the alloys had multiphase structure composed of (La, Mg)2Ni7, LaNi5 and small amount of LaNi2 phases. The discharge capacity of the alloys first increased and then decreased with increasing Co content. At a discharge current density of 900 mA/g, the HRD of the alloy electrodes increased from 81.3% (x=0) to 89.2 % (x=0.2), and then reduced to 87.8 % (x=0.6). After 60 charge/discharge cycles, the capacity retention rate of the alloys enhanced from 52.67% to 61.32%, and the capacity decay rate of the alloys decreased from 2.60 to 2.05 mAh/g per cycle with increasing Co content. The obtained results by XPS and XRD showed that the fundamental reasons for the capacity decay of the La-Mg-Ni system (Ce2Ni7-type) alloy electrodes were corrosion and oxidation as well as passivation of Mg and Lain alkaline solution.展开更多
The La-Mg-Ni system PuNi3-type La0.5Ce0.2Mg0.3Co0.4Ni2.6-xMnx(x=0,0.1,0.2,0.3,0.4) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the rapid quenching on the structure and electroc...The La-Mg-Ni system PuNi3-type La0.5Ce0.2Mg0.3Co0.4Ni2.6-xMnx(x=0,0.1,0.2,0.3,0.4) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the rapid quenching on the structure and electrochemical characteristics of the alloys were studied. The results obtained by XRD,SEM and TEM indicate that the as-cast and quenched alloys mainly consist of two major phases,(La,Mg)Ni3 and LaNi5,as well as a residual phase LaNi. The rapid quenching does not exert an obvious influence on the phase composition of the alloys,but it leads to an increase of the LaNi5 phase and a decrease of the(La,Mg)Ni3 phase. The as-quenched alloys have a nano-crystalline structure,and the grain sizes of the alloys are in the range of 20-30 nm. The results by the electrochemical measurements indicate that both the discharge capacity and the high rate discharge(HRD) ability of the alloy first increase and then decrease with the variety of quenching rate and obtain the maximum values at the special quenching rate which is changeable with the variety of Mn content. The rapid quenching significantly improves the cycle stabilities of the alloys,but it slightly impairs the activation capabilities of the alloys.展开更多
In order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys,Ni in the alloy is substituted by element Co. The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox (x=0,0.1,0.2,0.3,0.4) alloys w...In order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys,Ni in the alloy is substituted by element Co. The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox (x=0,0.1,0.2,0.3,0.4) alloys were synthesized by melt-spinning technique. The structures of the as-cast and spun alloys were studied with an X-ray diffractometer (XRD) and a high resolution transmission electronic microscope (HRTEM). An investigation on the thermal stability of the as-spun alloys was carried out with a differential scanning calorimeter (DSC). The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results demonstrate that the substitution of Co for Ni does not alter the major phase of Mg2Ni but results in the formation of secondary phase MgCo2. No amorphous phase is detected in the as-spun Co-free alloy,but a certain amount of amorphous phase is clearly found in the as-spun Co-containing alloys. The substitution of Co for Ni exerts a slight influence on the hydriding kinetics of the as-spun alloy. However,it dramatically enhances the dehydriding kinetics of the as-cast and spun alloys. As Co content (x) increases from 0 to 0.4,the hydrogen desorption capacity increases from 0.19% to 1.39% (mass fraction) in 20 min for the as-cast alloy,and from 0.89% to 2.18% (mass fraction) for the as-spun alloy (30 m/s).展开更多
文摘The glass-ceramics were prepared with the spodumene mineral as the main raw material,and the effects of ZrO_(2)replacing TiO_(2)on the samples were systematically investigated.The results show that the substitution of ZrO_(2)for TiO_(2)is not conductive to precipitate𝛽β-quartz solid solution phase,but can improve the transparency and flexural strength of glass-ceramics.And the glass-ceramic with the highest visible light transmittance(87%)and flexural strength(231.80 MPa)exhibits an ultra-low thermal expansion of-0.028×10^(-7)K^(-1)in the region of 30-700℃.
基金the National Natural Science Foundation of China(Nos.51871125,51761032,52001005 and 51731002)Major Science and Technology Innovation Projects in Shandong Province(No.2019JZZY010320)for financial support of the work.
文摘Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.
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 La0.8Mg0.2Ni3.3Co0.2Six(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 °C)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.
文摘The effects of Co as a substituent for Ni on microstructure and electrochemical capacity of hydrogen storage alloys MI(NiCoMnAl)5.4 at -30- +80 ℃, in which the content of Co was 0, 1.31%, 2.63%, 3.94%, 5.25%, and 6.56% (mass fraction), respectively, were reported. All of the alloys were prepared by vacuum induction melting followed by melt-spinning. It is found that the electrochemical capacity of alloys at different temperature depends upon the compositions and preparation methods. The electrochemical capacity of alloys increases at higher temperature (40 - 80 ℃ ) and decreases at lower temperature ( - 30 - 0 ℃ ) with an increasing cobalt content. With an increasing temperature, melt-spinning is more favorable for improved capacity of the alloys than casting. Analyses of the charging/discharging potential curves illustrate that higher cobalt content and melt-spinning techniques are more effective to increase the capacity at higher temperature because of the higher hydrogen evolution potential. On the contrary, the capacity of alloys at lower temperature can be increased by decreasing cobalt content and casting, which is ascribed to higher hydrogen evolution potential and delayed hydrogen evolution reaction, as well as reduced potential drop in the charging/discharging process. XRD patterns confirm that all of the specimens present a single hexagonal CaCu5-type structure and an increased lattice parameters with increasing Co content. The FWHM of the main peak of melt-spun ribbons reduces because of more homogeneous composition and less lattice strain defects.
基金This work was financially supported by National Natural Science Foundations of China (No.50131040)Key Technologies R & D Program of Inner Mongolia (No.20050205)College Scientific Research Project of Inner Mongolia (No.NJ05064).
文摘In order to improve the cycle stability of La-Mg-Ni-Co type alloy electrode, rapid quenching technology was employed. The effects of rapid quenching on the microstructure and cycle stability of the alloy were investigated. The obtained results show that the La2Mg(Ni0.85Co0.15)9M0.1 (M=B, Cr) alloy electrodes are composed of (La, Mg)Ni3 phase, LaNi5 phase and a small amount of the LaNi2 phase. A trace of the Ni2B phase exists in the as-cast MB alloy, and the Ni2B phase in the alloy nearly disappears after rapid quenching. Rapid quenching technology can slightly improve the cycling life of the alloy. When the quenching rate increases from 0 m·s-1 (As-cast is defined as quenching rate of 0 m·s-1) to 30 m·s-1, the cycle lives of the MB, MCr alloys enhance from 86 and 87 cycles to 106 and 119 cycles, respectively. On the other hand, the average capacity decay rates of the MB, MCr alloys decrease from 1.7172 and 1.7178 mAh·g-1·cycle-1 to 1.5751 and 1.3060 mAh·g-1·cycle-1 after 86 charge-discharges cycling, respectively.
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,China(Nos.2011ZD10 and 2010ZD05)
文摘In order to ameliorate the electrochemical hydrogen storage performances of La-Mg–Ni system A_2B_7-type electrode alloys, the partial substitution of M (M = Zr, Pr) for La was performed. The melt spinning technology was used to fabricate the La_(0.75-x)M_xMg_0.25Ni_3.2Co_0.2Al_0.1 (M = Zr, Pr; x = 0, 0.1) electrode alloys. The influences of the melt spinning and substituting La with M (M = Zr, Pr) on the structures and the electrochemical hydrogen storage characteristics of the alloys were investigated. The analysis of XRD, SEM, and TEM reveals that the as-cast and spun alloys have a multiphase structure composed of two main phases (La, Mg)_2Ni_7 and LaNi_5 as well as a residual phase LaNi_2 . The as-spun (M = Pr) alloy displays an entire nanocrystalline structure, while an amorphous-like structure is detected in the as-spun (M = Zr) alloy, implying that the substitution of Zr for La facilitates the amorphous formation. The electrochemical measurements exhibit that the substitution of Pr for La clearly increases the discharge capacity of the alloys; however, the Zr substitution brings on an adverse impact. Meanwhile, the M (M = Zr, Pr) substitution significantly enhances its cycle stability. The melt spinning exerts an evident effect on the electrochemical performances of the alloys, whose discharge capacity and high rate discharge ability (HRD) first mount up and then fall with the growing spinning rate, whereas their cycle stabilities monotonously augment as the spinning rate increases.
基金Project(2006AA05Z132) supported by the National 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 Natural Science Foundation of Inner Mongolia,ChinaProject(NJzy08071) supported by High Education Science Research Program of Inner Mongolia,China
文摘The Mg2Ni-type alloys with nominal compositions of Mg20Ni10-xCox(x=0,1,2,3,4,%,mass fraction) were prepared by melt-spinning technology.The structures of the alloys were studied by XRD,SEM and HRTEM.The hydrogen absorption/desorption kinetics and the electrochemical performances of the alloys were measured.The results show that no amorphous phase forms in the as-spun Co-free alloy,but the as-spun alloys containing Co show a certain amount of amorphous phase.The hydrogen absorption capacities of the as-cast alloys first increase and then decrease with the incremental change of Co content.The hydrogen desorption capacities of as-cast and spun alloys rise with increasing Co content.The melt spinning significantly improves the hydrogenation and dehydrogenation capacities and kinetics of the alloys.The substitution of Co for Ni clearly enhances the discharge capacities of the alloys and the cycle stability of the as-spun alloys.
基金Projects(50871050, 50961009) supported by the National Natural Science Foundation of ChinaProject(2010ZD05) supported by the Natural Science Foundation of Inner Mongolia, ChinaProject(NJzy08071) supported by the Higher Education Science Research Project of Inner Mongolia, China
文摘In order to improve the electrochemical hydrogen storage performance of the Mg2Ni-type electrode alloys, Mg in the alloy was partially substituted by La, and the nanocrystalline and amorphous Mg2Ni-type Mg20-xLaxNi10 (x=0, 2) alloys were synthesized by melt-spinning technique. The microstructures of the as-spun alloys were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical hydrogen storage properties of the experimental alloys were tested. The results show that no amorphous phase is detected in the as-spun Mg20Ni10 alloy, but the as-spun Mg18La2Ni10 alloy holds a major amorphous phase. As La content increases from 0 to 2, the maximum discharge capacity of the as-spun (20 m/s) alloys rises from 96.5 to 387.1 mA·h/g, and the capacity retaining rate (S20) at the 20th cycle grows from 31.3% to 71.7%. Melt-spinning engenders an impactful effect on the electrochemical hydrogen storage performances of the alloys. With the increase in the spinning rate from 0 to 30 m/s, the maximum discharge capacity increases from 30.3 to 135.5 mA·h/g for the Mg20Ni10 alloy, and from 197.2 to 406.5 mA·h/g for the Mg18La2Ni10 alloy. The capacity retaining rate (S20) of the Mg20Ni10 alloy at the 20th cycle slightly falls from 36.7% to 27.1%, but it markedly mounts up from 37.3% to 78.3% for the Mg18La2Ni10 alloy.
基金863 Program (2006AA05Z132)the National Natural Science Foundation of China (50642033)+1 种基金Natural Science Founda-tion of Inner Mongolia, China (200711020703)Science and Technology Planned Project of Inner Mongolia, China (20050205)
文摘Aiming at the improvement of the cyclic stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloy was partly substituted by Fe. The electrode alloys of La0.7Mg0.3Co0.45Ni255-xFex (x=0, 0.1, 0.2, 0.3, 0.4) were prepared by casting and rapid quenching. The influence of the quenching on cyclic stability as well as structure of the alloys was investigated in detail. The results of electrochemical measurement indicated that rapid quenching significantly improved cyclic stability. When the quenching rate rose from 0 (As-cast was defined as a quenching rate of 0 m/s) to 30 m/s, the cyclic life of Fe-free alloy (x=-0) increased from 81 to 105 cycles, and for alloy containing Fe(x=0.4), it grew from 106 to 166 cycles at a current density of 600 mA/g. The results obtained by XRD, TEM and SEM revealed that the as-cast and quenched alloys had multiphase structures, including two major phases (La, Mg)Ni3 and LaNi5 as well as an imptLrity phase LaNi2. Rapid quenching helped the formation of an amorphous-like structure in Fe containing alloys.
基金Projects(51161015,50961009) supported by the National Natural Science Foundation of ChinaProject(2011AA03A408) supported by the National High Technology Research and Development Program of ChinaProjects(2011ZD10,2010ZD05) supported by the Natural Science Foundation of Inner Mongolia,China
文摘For the purpose of improving the electrochemical cycle stability of the La-Mg-Ni based A2B7-type electrode alloys, both reducing Mg content and substituting La with Pr were adopted. The La0.8-xPrxMg0.2Ni3.15Co0.2Al0.1Si0.05 (x=0, 0.1, 0.2, 0.3, 0.4) electrode alloys were fabricated by casting and annealing. The investigation on the structures and electrochemical performances of the alloys was performed. The obtained results reveal that the as-cast and annealed alloys comprise two major phases, (La,Mg)2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu 5-type structure, as well as a little residual LaNi3 phase. It is also found that the addition of Pr element observably affects the electrochemical hydrogen storage characteristics of the alloys, just as the discharge capacity and high rate discharge ability (HRD) first rise then fall with the growing of Pr content, and among all the alloys, the as-cast and annealed (x=0.3) alloys generate the largest discharge capacities of 360.8 and 386.5 mA·h/g, respectively. Additionally, the electrochemical cycle stability of all the alloys markedly grows with the increase of Pr content. The capacity retaining rate (S100 ) at the 100th charging and discharging cycle is enhanced from 64.98% to 77.55% for the as-cast alloy, and from 76.60% to 95.72% for the as-annealed alloy by rising Pr content from 0 to 0.4. Furthermore, the substitution of Pr for La results in first increase and then decrease in the hydrogen diffusion coefficient (D), the limiting current density (IL ) as well as the electrochemical impedance.
基金Projects(51161015,51371094)supported by National Natural Science Foundations of ChinaProject(2011ZD10)supported by Natural Science Foundation of Inner Mongolia,China
文摘In this work,a comprehensive comparison regarding the impacts of M(M=Cu,Co,Mn)substitution for Ni on the structures and the hydrogen storage kinetics of the nanocrystalline and amorphous Mg20Ni10-xMx(M=Cu,Co,Mn; x=0-4)alloys prepared by melt spinning has been carried out.The analysis of XRD and TEM reveals that the as-spun(M=None,Cu)alloys display an entire nanocrystalline structure,whereas the as-spun(M=Co,Mn)alloys hold a mixed structure of nanocrystalline and amorphous structure when M content x=4,indicating that the substitution of M(M=Co,Mn)for Ni facilitates the glass formation in the Mg2Ni-type alloy.Besides,all the as-spun alloys have a major phase of Mg2Ni but M(M=Co,Mn)substitution brings on the formation of some secondary phases,MgCo2 and Mg phases for M=Co as well as MnNi and Mg phases for M=Mn.Based upon the measurements of the automatic Sieverts apparatus and the automatic galvanostatic system,the impacts engendered by M(M=Cu,Co,Mn)substitution on the gaseous and electrochemical hydrogen storage kinetics of the alloys appear to be evident.The gaseous hydriding kinetics of the alloys first rises and then declines with the growing of M(M=Cu,Co,Mn)content.Particularly,the M(M= Mn)substitution results in a sharp drop in the hydriding kinetics when x=4.The M(M=Cu,Co,Mn)substitution ameliorates the dehydriding kinetics dramatically in the order(M=Co)>(M=Mn)>(M=Cu).The electrochemical kinetics of the alloys visibly grows with M content rising for(M=Cu,Co),while it first increases and then declines for(M=Mn).
基金Funded by National Natural Science Foundations of China(Nos.51161015 and 50961009)Natural Science Foundation of Inner Mongolia,China(Nos.2011ZD10 and 2010ZD05)Higher Education Science Research Project of Inner Mongolia,China(No.NJzy08071)
文摘The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox (x = 0, 0.1, 0.2, 0.3, 0.4) alloys were synthesized by melt quenching technology. The structures of the as-cast and quenched alloys were characterized by XRD, SEM and HRTEM. The gaseous hydrogen storage kinetics of the alloys was measured using an automatically controlled Sieverts apparatus. The alloy electrodes were charged and discharged with a constant current density in order to investigate the electrochemical hydrogen storage kinetics of the alloys. The results demonstrate that the substitution of Co for Ni results in the formation of secondary phases MgCo2 and Mg instead of altering the major phase Mg2Ni. No amorphous phase is detected in the as-quenched Co- ffee alloy, however, a certain amount of amorphous phase is clearly found in the as-quenched alloys substituted by Co. Furthermore, both the rapid quenching and the Co substitution significantly improve the gaseous and electrochemical hydrogen storage kinetics of the alloys, for which the notable increase of the hydrogen diffusion coefficient (D) along with the limiting current density (IL) and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible.
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.
基金This work was financially supported by National Natural Science Foundation of China ( No.50131040)Science and Technology Planned Project of Inner Mongolia, China ( No.20050205)Higher Education Science Research Project ofInner Mongolia, China (No.NJ05064)
文摘In order to improve the electrochemical cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloys was partially substituted by M (M=Cu, Al, Mn). A new La-Mg-Ni system electrode alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Cu, Al, Mn; x=0, 0.1) were prepared by casting and rapid quenching. The effects of element substitution and rapid quenching on the microstructures and electrochemical performances of the alloys were investigated. The results by XRD, SEM and TEM show that the alloys have a multiphase structure, including the (La, Mg)Ni3 phase, the LaNi5 phase and the LaNi2 phase. The rapid quenching and element substitution have an imperceptible influence on the phase compositions of the alloys, but both change the phase abundance of the alloys. The rapid quenching significantly improves the composition homogeneity of the alloys and markedly decreases the grain size of the alloys. The Cu substitution promotes the formation of an amorphous phase in the as-quenched alloy, and a reversal result by the Al substitution. The electrochemical measurement indicates that the element substitution decreases the discharge capacity of the alloys, whereas it obviously improves the cycle stability of the alloys. The positive influence of element substitution on the cycle life of the alloys is in sequence Al>Cu>Mn, and negative influence on the discharge capacity is in sequence Al>Mn>Cu. The rapid quenching significantly enhances the cycle stability of the alloys, but it leads to a different extent decrease of the discharge capacity of the alloys.
基金the National Natural Science Foundation of China (50701011)Natural Science Foundation of Inner Mongolia, China (200711020703)Science and Technology Planned Project of Inner Mongolia, China (20050205)
文摘In order to improve the cyclic stability of La-Mg-Ni system (Ce2Ni7-type) alloy electrode, small amount of Co was added in La0.75Mg0.25Ni3.5 alloy. The effect of Co on electrochemical performance and microstructure of the alloys were investigated in detail. XRD results showed that the alloys had multiphase structure composed of (La, Mg)2Ni7, LaNi5 and small amount of LaNi2 phases. The discharge capacity of the alloys first increased and then decreased with increasing Co content. At a discharge current density of 900 mA/g, the HRD of the alloy electrodes increased from 81.3% (x=0) to 89.2 % (x=0.2), and then reduced to 87.8 % (x=0.6). After 60 charge/discharge cycles, the capacity retention rate of the alloys enhanced from 52.67% to 61.32%, and the capacity decay rate of the alloys decreased from 2.60 to 2.05 mAh/g per cycle with increasing Co content. The obtained results by XPS and XRD showed that the fundamental reasons for the capacity decay of the La-Mg-Ni system (Ce2Ni7-type) alloy electrodes were corrosion and oxidation as well as passivation of Mg and Lain alkaline solution.
基金Project(2006AA05Z132) supported by the Hi-tech Research and Development Program of ChinaProject(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 Higher Education Science Research Project of Inner Mongolia, China
文摘The La-Mg-Ni system PuNi3-type La0.5Ce0.2Mg0.3Co0.4Ni2.6-xMnx(x=0,0.1,0.2,0.3,0.4) hydrogen storage alloys were prepared by casting and rapid quenching. The effects of the rapid quenching on the structure and electrochemical characteristics of the alloys were studied. The results obtained by XRD,SEM and TEM indicate that the as-cast and quenched alloys mainly consist of two major phases,(La,Mg)Ni3 and LaNi5,as well as a residual phase LaNi. The rapid quenching does not exert an obvious influence on the phase composition of the alloys,but it leads to an increase of the LaNi5 phase and a decrease of the(La,Mg)Ni3 phase. The as-quenched alloys have a nano-crystalline structure,and the grain sizes of the alloys are in the range of 20-30 nm. The results by the electrochemical measurements indicate that both the discharge capacity and the high rate discharge(HRD) ability of the alloy first increase and then decrease with the variety of quenching rate and obtain the maximum values at the special quenching rate which is changeable with the variety of Mn content. The rapid quenching significantly improves the cycle stabilities of the alloys,but it slightly impairs the activation capabilities of the alloys.
基金Project(2006AA05Z132) supported by the National High-tech Research and Development Program of ChinaProjects(50871050, 50961009) supported by the National Natural Science Foundation of China+1 种基金Project(2010ZD05) supported by the Natural Science Foundation of Inner Mongolia, ChinaProject(NJzy08071) supported by the High Education Science Research Program of Inner Mongolia, China
文摘In order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys,Ni in the alloy is substituted by element Co. The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xCox (x=0,0.1,0.2,0.3,0.4) alloys were synthesized by melt-spinning technique. The structures of the as-cast and spun alloys were studied with an X-ray diffractometer (XRD) and a high resolution transmission electronic microscope (HRTEM). An investigation on the thermal stability of the as-spun alloys was carried out with a differential scanning calorimeter (DSC). The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results demonstrate that the substitution of Co for Ni does not alter the major phase of Mg2Ni but results in the formation of secondary phase MgCo2. No amorphous phase is detected in the as-spun Co-free alloy,but a certain amount of amorphous phase is clearly found in the as-spun Co-containing alloys. The substitution of Co for Ni exerts a slight influence on the hydriding kinetics of the as-spun alloy. However,it dramatically enhances the dehydriding kinetics of the as-cast and spun alloys. As Co content (x) increases from 0 to 0.4,the hydrogen desorption capacity increases from 0.19% to 1.39% (mass fraction) in 20 min for the as-cast alloy,and from 0.89% to 2.18% (mass fraction) for the as-spun alloy (30 m/s).