Gaseous and electrochemical hydrogen storage kinetics of as-quenched nanocrystalline and amorphous Mg2Ni-type alloys

The nanocrystalline and amorphous Mg₂Ni-type Mg₂Ni_1?x Co _x (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 Cofree 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 (I _L ) and the obvious decline of the electrochemical impedance generated by both the Co substitution and the rapid quenching are basically responsible.     

Influences of melt spinning on electrochemical hydrogen storage performance of nanocrystalline and amorphous Mg2Ni-type alloys

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 Mg_20−x La _x Ni₁₀ (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 (S ₂₀) 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 (S ₂₀) 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.     

Influence of substituting Ni with Co on hydriding and dehydriding kinetics of melt spun nanocrystalline and amorphous Mg2Ni-type alloys

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 Mg₂Ni_1−x Co _x (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).     

Hydriding and dehydriding kinetics of nanocrystalline and amorphous MgzNi1-xMnx （x=0-0.4） alloys prepared by melt spinning

A partial substitution of Ni by Mn was implemented in order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys.The nanocrystalline and amorphous Mg2Ni-type Mg2Ni1-xMnx(x=0,0.1,0.2,0.3,0.4) alloys were synthesized by the melt-spinning technique.The structures of the as-cast and spun alloys were studied by X-ray diffractometry(XRD),scanning electron microscopy(SEM) and high resolution transmission electron microscopy(HRTEM).The hydrogen absorption and desorption kinetics of the alloys ...     

Effects of alloying side B on Ti-based AB2 hydrogen storage alloys

Ti-based AB2-type hydrogen storage alloys are a group of promising materials, which will probably replace the prevalent rare earth-based AB5-type alloys and be adopted as the main cathode materials of nickelmetal hydride (Ni-MH) batteries in the near future. Alloying in side B is a major way to improve the performance of Ti-based AB2-type alloys. Based on recent studies, the effects of alloying elements in side B upon the performance of Ti-based AB2-type hydrogen storage alloys are systematically reviewed here. These performance sare divided into two categories, namely PCI characteristics, including hydrogen storage capacity (HSC), plateau pressure (PP), pressure hysteresis (PH) and pressure plateau sloping (PPS), and electrochemical properties, including discharge capacity (DC), activation property ( AP), cycling stability (CS) and high-rate dischargeability (HRD). Furthermore, the existing problems in these investigations and some suggestions for future research are proposed.     

Effect of VFe addition on hydrogen storage behavior of TiMn1.5-based alloys

The hydrogen absorption and desorption behavior of TiMn1.25Cr0.25 alloys with VFe substitution for partial Mn was investigated at 273, 293 and 313 K. It is found that VFe substitution increases their hydrogen storage capacity, decreases the plateau pressure and the hysteresis factor of their pressure-composition-temperature (PCT) curves. After annealing treatment at 1223 K for 6 h, TiMn0.95Cr0.25(VFe)0.3 alloy exhibits a lower hydrogen desorption plateau pressure (0.27 MPa at 313 K) and a smaller hysteresis factor (0.13 at 313 K); the maximum and effective hydrogen storage capacities (mass fraction) are 2.03% and 1.12% respectively, which can satisfy the demand of hydrogen storage tanks for proton exchange membrane fuel cells (PEMFC).     

Effect of stoichiometry and Cu-substitution on the phase structure and hydrogen storage properties of Ml-Mg-Ni-based alloys

To improve the electrochemical properties of rare-earth–Mg–Ni-based hydrogen storage alloys, the effects of stoichiometry and Cu-substitution on the phase structure and thermodynamic properties of the ...     

LaxMm1-x(NiCoMnCuAl)5.1贮氢合金的电化学性能

在低钴AB5型贮氢合金LaxMm1-x(NiCoMnCuAl)5．1(x=0．25，0．38，0．56，0．74)中，加入纯La调整富Ce混合稀土中的La含量，测试了合金的电化学性能，研究了La含量的变化对LaxMm1-x(NiCoMnCuAl)5．1合金晶格参数、热力学参数及电化学性能的影响。结果表明，合金的晶格常数、晶胞体积及标准生成焓的绝对值随La含量的增加而增大，La含量的增加对提高铸态及快淬态合金的容量有利，但使得电化学循环稳定性及放电平台压下降，La含量的变化对合金的活化性能基本没有影响，铸态和快淬态合金通过1～2次循环均可完全活化。     

熔炼掺杂对AB5型贮氢合金的结构和性能影响

为了探索一种新的掺杂方式对AB5型贮氢合金性能的影响,采用熔炼掺杂方法,研究了掺杂适量TiMn1.5合金(掺杂量为4％、8％的TiMn1.5)对成分为La0.7Ni2.65Co0.75Mn0.1的AB5型贮氢合金的结构及性能影响.XRD测试结果证实:掺杂后合金的主相仍为LaNi5相,生成了少量(NiCo)3 Ti相.(...     

熔炼掺杂对AB5型贮氢合金的结构和性能影响

为了探索一种新的掺杂方式对AB5型贮氢合金性能的影响,采用熔炼掺杂方法,研究了掺杂适量TiMn1.5合金（掺杂量为4％、8％的TiMn1.5）对成分为‰．La0.7Ni2.65Co0.75Mn0.1的AB5型贮氢合金的结构及性能影响。XRD测试结果证实：掺杂后合金的主相仍为LaNi5相,生成了少量（NiCo）2Ti相。（NiCo）3Ti相的出现对贮氢合金的气态和电化学贮氢性能都有不同程度的降低。合金电极的动力学测试结果表明（线性扫描法和交流阻抗法）：在0．5～2．5C的放电电流密度,掺杂前后的合金电极的反应速率均由电极表面电荷转移速率决定,掺杂4％TiMn1.5的合金样品电极的高倍率放电性能有一定的改善。在3C放电电流密度以上,电极反应速率均由氢扩散速率来控制,随着TiMn1.5的掺杂的增加,其合金电极的高倍率性能降低。     

快凝对MmNi5-x(CoMn)x合金电化学性能的影响

利用熔体淬冷法制备出不同速度下的4种合金薄带,研究了快凝对贮氢合金电化学性能的影响.合金的晶体结构采用XRD和SEM进行表征.结果显示,铸态和快凝合金都是单一的CaCu5相结构,快凝后的合金组织变得更加细密,晶粒变小而且更加均匀.电化学实验结果表明,快凝显著提高了合金的稳定性,但是降低了合金的放电容量和高倍率性能,铸态...     

升温速率对沥青燃烧和气态产物释放特性的影响

采用热重-傅里叶变换红外光谱联用实验分析不同升温速率下沥青燃烧的失重过程,得到沥青燃烧过程中气态产物的析出规律,并利用Kissinger法计算沥青燃烧的动力学参数,为揭示火灾中沥青的燃烧机理和指导阻燃抑烟沥青设计提供重要的理论依据. 结果表明,沥青燃烧过程主要包括有氧热解和重质组分燃烧2个阶段,且两阶段的反应机理不同. 沥青有氧热解阶段包含3个失重峰,分别对应饱和分、芳香分和胶质的热解,3种成分燃烧的活化能依次增大;随着升温速率的增大,3个失重峰出现重叠,最大失重速率明显增加,气态产物的红外光谱吸收峰强度逐渐增强. 重质组分燃烧阶段的活化能相比胶质有氧热解更低,最大失重速率及红外光谱吸收峰强度随升温速率变化不大.     

退火处理对Ti-Zr-Cu-Be块体非晶合金力学性能的影响

采用铜模铸造法制备了直径为2mm的Ti55-xZr10+xBe27.5Cu7.5(x=0,10,20)块体非晶合金,并对其进行等温退火处理.利用X射线衍射(XRD)、扫描电镜(SEM)、差氏扫描量热仪(DSC)及压缩试验等方法研究了非晶合金的相结构、显微组织和热稳定性,以及退火处理对其力学性能的影响.结果表明:该系列合金在553 K及583 K下保温长达5 h时间内依然表现为非晶态.退火处理后,Ti35Zr30Be27.5Cu7.5合金屈服强度、断裂强度均提到了提高,其中在583 K下保温1 h后屈服强度、断裂强度分别达到了1 921、2 169 MPa;其塑性由处理前的3.47%提高到了6.57%.Ti45Zr20Be27.5Cu7.5合金在退火后其力学性能变化不明显.Ti55Zr10Be27.5Cu7.5合金随着退火温度及保温时间的增加其屈服强度、断裂强度及塑性均明显降低.     

LaNi_(3.15-x)Mn_xCo_(0.25)Al_(0.1)储氢合金结构及电化学性能

为了研究Mn替代Ni对AB3.5型储氢合金结构及电化学性能的影响,采用电弧炉熔炼制备LaNi3.15-xMnxCo0.25Al0.1合金。采用XRD、SEM等材料分析方法以及恒电流充放电等电化学测试技术,研究LaNi3.15-xMnxCo0.25Al0.1(0≤x≤0.3)合金的结构和电化学储氢性能。结果表明:LaNi3.15-xMnxCo0.25Al0.1(0≤x≤0.3)合金由多相组合形成,合金的主相为LaNi5和La2Ni7;随着Mn替代Ni含量的增加,LaNi5相中a轴和c轴以及晶胞体积增加;合金电极的最大放电容量有所升高,由x=0的238mA·h/g逐渐增加到x=0.3的277.1mA·h/g;高倍率性能随着Mn含量的增加先升高后降低,在x=0.2时合金的高倍率性能最佳。     

Highly Improved Electrochemical Performances of the Nanocrystalline and Amorphous Mg_2Ni-type Alloys by Substituting Ni with M (M=Cu,Co,Mn)

The element Ni in the Mg_2Ni alloy is partially substituted by M(M = Cu, Co, Mn) in order to ameliorate the electrochemical hydrogen storage performances of Mg_2Ni-type electrode alloys. The nanocrystalline and amorphous Mg_(20)Ni_(10-x)M_x(M = None, Cu, Co, Mn; x = 0-4) alloys were prepared by melt spinning. The effects of the M(M = Cu, Co, Mn) content on the structures and electrochemical hydrogen storage characteristics of the as-cast and spun alloys were comparatively studied. The analyses by XRD, SEM and HRTEM reveal that all the as-cast alloys have a major phase of Mg_2Ni but the M(M = Co, Mn) substitution brings on the formation of some secondary phases, MgCo_2 and Mg for the(M = Co) alloy, and Mn Ni and Mg for the(M = Mn) alloy. Besides, the as-spun(M = None, Cu) alloys display an entirely nanocrystalline structure, whereas the as-spun(M = Co, Mn) alloys hold a nanocrystalline/amorphous structure, suggesting that the substitution of M(M = Co, Mn) for Ni facilitates the glass formation in the Mg_2Ni-type alloys. The electrochemical measurements indicate that the variation of M(M = Cu, Co, Mn) content engenders an obvious effect on the electrochemical performances of the as-cast and spun alloys. To be specific, the cyclic stabilities of the alloys augment monotonously with increasing M(M = Cu, Co, Mn) content, and the capacity retaining rate(S20) is in an order of(M = Cu) (M = Co) (M = Mn) (M = None) for x≤1 but changes to(M = Co) (M = Mn) (M = Cu) (M = None) for x≥2. The discharge capacities of the as-cast and spun alloys always grow with the rising of M(M = Co, Mn) content but first mount up and then go down with increasing M(M = Cu) content. Whatever the M content is, the discharge capacities are in sequence:(M = Co) (M = Mn) (M = Cu) (M = None). The high rate discharge abilities(HRDs) of all the alloys grow clearly with rising M(M = Cu, Co) content except for(M = Mn) alloy, whose HRD has a maximum value with varying M(M = Mn) content. Furthermore, for the as-cast alloys, the HRD is in order of(M = Co) (M = Mn) (M = Cu) (M = None), while for the as-spun(20 m·s~(-1)) alloys, it changes from(M = Co) (M = Mn) (M = Cu) (M = None) for x = 1 to(M = Cu) (M = Co) (M = None) (M = Mn) for x = 4.     

气体雾化AB5型贮氢合金微观结构特征及电化学性能

用气体雾化方法可以制备具有CaCu5型六方晶体结构MmNi5-x(CoMnAl)x的球形贮氢合金粉．其贮氢合金表面存在氧化层．气体雾化合金需要较长周期才能充分活化，然而气体雾化合金的循环寿命明显优于机械球磨合金．     

Thermoelectric properties of quaternary Mg_2Sn_(0.4)Si_(0.6-x)Ge_x alloys

Quaternary alloys Mg2Sn0.4Si0.6-xGex(x=0,0.02,0.05,0.08 0.1,and 0.2) were prepared using induction melting followed by hot-pressing.Relative densities of the sintered samples were over 97% of the theoretical values.Multiple phases were detected in the samples.It was found that the Seebeck coefficient was sensitive to the content of Mg2Ge and a maximum value of about 350 μV·K-1 was obtained.The introduction of Ge increases the electrical conductivity and the thermal conductivity simultaneously.The mechanism ...     

Effect of Cu doping and annealing treatment on the microstructure and magnetic properties of nanocrystalline single-phase Nd-Fe-B alloys

The effects of Cu addition and annealing treatment on the magnetic properties and microstructure of Nd12.3Fe81.7-xCuxB6 (x=0-1.2) ribbons melt-spun and annealed were systematically investigated by the methods of vibrating sample magnetometer (VSM), X-ray diffraction (XRD), and transmission electron microscopy (TEM). Optimum magnetic properties were achieved by annealing melt-spun Nd12.3Fe81.5Cu0.2B6 ribbons at 550°C for 15 min, which only contained Nd2Fe14B phase. The remanence, coercive force, and maximum ...     

铸态及快淬态La2Mg(Ni0.85Co0.15)9Crx(x=0～0.4)贮氢合金的电化学性能

为了提高La-Mg-Ni系(PuNi3型)贮氢合金的电化学循环稳定性,在La2Mg(Ni0.85Co0.15)9合金中加入微量Cr,用铸造及快淬工艺制备了La2Mg(Ni0.85Co0.15)9Crx(x=0,0.1,0.2,0.3,0.4)贮氢合金.研究了Cr含量对铸态及快淬态合金微观结构及电化学性能的影响.XRD,SEM及TEM的分析结果表明,铸态及快淬态合金具有多相结构,包括(La,Mg)Ni3相(PuNi3型结构)、LaNi5相和一定量的LaNi2相.随Cr含量的增加,铸态合金中LaNi2相的量增加.电化学测试结果表明,Cr的加入提高了铸态及快淬态合金的循环稳定性,但使合金的容量下降.当Cr添加量从0增加到0.4时,铸态合金的容量从396.3 mAh/g下降到355.6 mAh/g,循环寿命从72次增加到97次;快淬态(30 m/s)合金的容量从364.2 mAh/g下降到334.2 mAh/g,循环寿命从100次增加到131次.Cr添加使铸态合金的放电电压特性和活化性能得到改善.