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.     

RE-Mg-Ni系A_2B_7型合金的循环稳定性及电化学贮氢动力学

为了改善La-Mg-Ni系A2B7电极合金的电化学循环稳定性,用Zr部分替代合金中的La,并采用熔体快淬技术制备了La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1(x=0,0.05,0.1,0.15,0.2)电极合金.用XRD,TEM分析了合金的微观结构,结果表明,快淬不含Zr合金具有完全的纳米晶结构,而快淬含Zr合金中出现明显的非晶相,证明Zr替代有利于提高合金的非晶形成能力.铸态及快淬态合金均具有多相结构,包括两个主相(La,Mg)2Ni7及LaNi5和残余相LaNi2,Zr替代及快淬导致LaNi5相增加和(La,Mg)2Ni7相减少.Zr替代及快淬处理显著提高了合金的电化学循环稳定性,但快淬明显降低Zr0.2合金的电化学贮氢动力学;随Zr替代量的增加,5 m/s快淬合金的电化学贮氢动力学先增加后降低.     

硼对稀土系AB5型贮氢合金电化学容量及循环寿命的影响

为了提高低钴AB5型贮氢合金的电化学循环稳定性，在MmNi3．8Co0.4Mn0.6Al0．2贮氢合金中加微量的硼．用真空快淬工艺制备了稀土系低钴AB5型MmNi3．8Co0．4Mn0．6Al0．2Bx(x=0，0．1，0．2，0．3，0．4)贮氢合金，分析测试了铸态及快淬态合金的电化学性能及微观结构，研究了硼对铸态及快淬态合金电化学容量及循环寿命的影响．结果表明，硼使铸态及快淬态MmNi3.8Co0.4Mn0．6Al0．2贮氢合金的电化学容量不同程度地降低，但使电化学循环稳定性大幅度提高．硼对电化学性能的影响主要是促进非晶相的形成．     

铸态及快淬态Mm(NiMnSiAlCu)4.3Co0.6-xFex(x=0～0.4)电极合金的电化学性能

用XRD,TEM及SEM测试了稀土基AB5型贮氢合金Mm(NiMnSiAlCu)4.3Co0.6-xFex(x=0～0.4) 的微观结构,并全面测试了合金在铸态及快淬态下的电化学性能.研究结果表明,铸态合金为双相结构,主相为CaCu5型相,还有少量Ce2Ni7相,经快淬处理后,第二相减少.对铸态合金,随Fe含量的增加,合金的容量有所降低,循环稳定性得到改善.对快淬态合金,当铁含量大于0.2时,合金的容量急剧下降,而循环稳定性大幅度增加.这主要是由于铁的加入使合金的微观结构发生了变化.     

La2Ca2Mg2Ni13-xCox贮氢合金的相结构和电化学性能

研究元素Co部分替代Ni对La2Ca2Mg2Ni13合金相结构和电化学性能的影响。结果表明,La2Ca2Mg2Ni13-xCox（x=0,0．25,0．5,0．75和1．0）系列合金主要由PuNi3型结构的（La,Ca,Mg）（Ni,Co）,相和CaCu5型结构的（La,Ca）（Ni,Co）,相组成,随合金中Co替代量x的增加,PuNi3型主相的含量先增加后降低。当x=0．75时,合金具有最高的放电容量360mA·h/g,并具有较好的循环稳定性。     

不同烧结工艺对贮氢合金LaMgNiCo的性能影响

借助XRD和SEM及EPMA研究La0.67Mg0.33Ni2.5Co0.5贮氢合金的烧结工艺对该合金的微观组织结构及电化学性能的影响。结果表明,在不同烧结条件下合金均由不含Mg的LaNi5相、富Mg的LaNi3相及一个贫Mg的LaNix（x=3.0-3.8）相三相组成。当烧结温度不超过1203k时合金主相为LaN i3相,当烧结温度超过1 203K,LaN i5相逐步成为主相。电化学性能分析结果表明,烧结温度不超过1203K,合金放电能力主要受合金组织形成与均匀性影响;而烧结温度超过1 203K,Mg元素挥发损失成为影响合金放电能力的决定因素。烧结条件为873k～1123k保持24 h、1203k保持2h,是制备La0.67Mg0.33Ni2.5Co0.5贮氢合金的适宜工艺。     

退火处理对La-Mg-Ni-Co合金电化学性能的影响

为了改善La-Mg-Ni-Co系贮氢电极合金的综合电化学性能，研究了退火处理对La0.7Mg0.3(Ni0.85Co0.15)3.4相结构和电化学性能的影响.在1 073 ～1 223 K下退火9 h制得样品，并进行了XRD分析以及恒电流充放电、线性极化和恒电位阶跃3种电化学测试.结果表明，铸态和退火态合金均由具有PuNi3结构的主相及少量杂相组成.退火态合金相的成分和结构均匀性得到明显改善，并具有较低的吸氢体积膨胀率.退火处理使合金的最大放电容量有所提高，循环稳定性得到明显改善.退火态合金放电容量的提高与合金中主相丰度的增大密切相关.合金循环稳定性的改善主要归结于退火态合金具有较低的吸氢体积膨胀率和较好的合金成分均匀性.     

快淬对贮氢合金组织和电化学性能的影响

通过XRD、TEM、DTA分析和电化学实验，研究了快淬对贮氢合金组织和电化学性能的影响，研究表明，成分均匀性改善和单胞体积减小是影响快淬氢合金电化学性能的主要因素，其中，前者使充放电循环稳定性提高，后者使放电容量降低，在本研究中，快淬速度为10m/s时，合金成分的均匀性已较铸态有明显改善，更高的快淬速度并不能使成分的均匀性进一步大幅度提高，反而使单胞体积减小，因此，快淬速度为10m/s时，快淬合金的综合电化学性能最佳。     

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。     

A2B7型La0.75Mg0.25Ni3.5-xCrx(x=0～0.3)贮氢合金相结构及电化学性能研究

采用感应熔炼方法制备了La0.75Mg0.25Ni3.5-xCrx(x=0,0.05,0.1,0.2,0.3)四元贮氢合金,系统地研究了合金B端Cr元素对Ni部分替代对合金相结构及电化学性能的影响.X衍射(XRD)分析表明,La0.75Mg0.25Ni3.5合金是由La2Ni7相组成.随着Cr元素的加入,该类合金中出现LaNi5相及LaNi3相,且随着Cr含量的增加而增多.电化学测试表明,随Cr含量的增加,合金电极活化次数变化不大,最大放电容量逐步降低,合金的最大放电容量由x=0.05时的383.43 mAh/g下降到x=0.3时的348.40 mAh/g;而合金的高倍率放电性能呈现先增后减的趋势,当电流密度为900 mA/g时,合金的高倍率放电性能由83.66%(x=0)增加到92.57%(x=0.05)然后减小到83.9%(x=0.3);循环稳定性先增加后下降,当x=0.1时合金电极的循环寿命达到最大(S100=74.71%).     

Microstructure and Hydrogen Absorption/Desorption Behavior of Mg_(23-x)La_xNi_(10) Alloy

Induction melting was used as a routine method to synthesize Mg_(23)Ni_(10), Mg_(22)LaNi_(10) and Mg_(21)La_2Ni_(10) alloys, and followed by a detailed microstructural characterization which included X-ray diffraction(XRD), scanning electron microscopy(SEM) with energy dispersive spectrometer(EDS), high resolution transmission electron microscope(HRTEM) and hydrogen absorption/desorption measurements. XRD analysis results showed that Mg_2Ni and Mg phases were detected in the XRD pattern of the Mg_(23)Ni_(10) alloy, however, the La addition results in conversion from Mg to LaMg_3 and La_2Mg_(17) phases and appearance of crystal defects included dislocations, twin grain boundary and vacancy in the Mg_(22)LaNi_(10) and Mg_(21)La_2Ni_(10) alloy textures. The total maximum hydrogen absorption capacity was 4.45 wt% for the Mg_(23)Ni_(10) alloy, however, the Mg_(22)LaNi_(10) and Mg_(21)La_2Ni_(10) alloys with vacancy, dislocations and twin grain boundary, absorbed 3.66 wt% and 3.60 wt%, respectively, indicating that the La addition led to decreasing of the maximum hydrogen absorption capacity. Besides, hydrogen absorption/desorption of 90% of saturated state expended for about 456 and 990 s for pristine Mg_(23)Ni_(10) alloy, by contrast, the time decreased owing to improvement of hydrogen absorption and desorption kinetics in the alloy with La element, with which the uptake time for hydrogen content to 90% of saturated state was 150 and 78 s, and 90% hydrogen can be released in 930 and 804 s for Mg_(22)LaNi_(10) and Mg_(21)La_2Ni_(10) alloys in the experimental condition.     

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.     

Mechanical properties and microstructure of as-cast and extruded Mg-（Ce, Nd）-Zn-Zr alloys

1INTRODUCTION Thebeneficialinfluenceofrareearth(RE)metalsontheambientandelevatedtemperature mechanicalpropertiesofmagnesiumalloyhaslongbeenrecognized[13].Recently,Yttriumisaddedto Magnesiumalloytoimproveitstensilestrength andcreepresistance,andsuchinvestigationsatheat resistantmagnesiumalloyhaveledtothede velopmentofWE43andWE54alloys[4,5].Al thoughsuchalloysexhibitgoodpropertiesupto573Kthroughcastingandextruding,therelativelyhighcostofYttriumrestrictstheapplicationof suchalloys.Otherr…     

Evolution of microstructures in Al-Mn-Mg alloys during homogenization

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Electrochemical Hydrogen Storage Performance of the Nanocrystalline and Amorphous Pr-Mg-Ni-based Alloys Synthesized by Mechanical Milling

The PrMg12-type composite alloy of PrMg₁₁Ni + x wt% Ni (x=100,200) with an amorphous and nanocrystalline microstructure were synthesized through the mechanical milling.Effects of milling duration and Ni content on the microstructures and electrochemical hydrogen storage performances of the ball-milled alloys were methodically studied.The ball-milled alloys obtain the optimum discharge capacities at the first cycle.Increasing Ni content dramatically enhances the electrochemical property of alloys.Milling time varying may obviously impact the electrochemical performance of these alloys.The discharge capacities show a significant upward trend with milling duration prolonging,but milling for a longer time more than 40 h induces a slight decrease in the discharge capacity of the x=200 alloy.As milling duration increases,the cycle stability clearly lowers,while it first declines and then augments under the same condition for the x=200 alloy.The high-rate discharge abilities of the ball-milled alloys show the optimum values with milling time varying.     

Sr对Mg-5Sn-5Zn铸造镁合金组织的影响

通过光学显微镜、扫描电镜和X射线衍射仪研究了Mg-5Sn-5Zn-xSr（x=0,0.5,1,2）4种铸造镁合金的显微组织和相组成.结果表明：在Mg-5Sn-5Zn合金中加入质量分数为0.5%～2%的Sr元素后,不但能够缩小α-Mg枝晶间距,而且还能形成三元相MgSnSr.随着Sr含量的增加,在晶界析出的Mg2Sn相减少,晶内的MgSnSr相增加。合金中的MgZn相与Mg2Sn相依附在一起,大多数的MgZn相以α-Mg＋MgZn相的共晶方式存在.     

凝固冷速与时效时间对CaMgSn形态的影响

针对CaMgSn形貌对Mg-Sn-Ca系合金的力学性能具有重要的影响,研究了慢冷、快冷及时效处理对CaMgSn组织形貌的影响规律.分别采用光学显微镜、扫描电镜、X射线衍射仪和维氏硬度计对比分析了不同处理条件对Mg-3Sn-2Ca-3Cu（质量分数/%）合金微观组织、相结构和硬度的影响.Mg-3Sn-2Ca-3Cu合金慢冷组织主要由α-Mg、CaMgSn、Mg2Ca、CuMg2和Mg2Sn构成,其中CaMgSn为粗大的棒状相;快冷及时效处理后,CaMgSn的形态发生了明显的改变,在时效48 h时,转变为近球状形貌.时效处理后,合金的维氏硬度得到了明显的提高,在时效48 h时达到最高值77.随时效时间延长,表现为硬度的降低和第二相与基体的脱离.     

Effects of Y Content on the Microstructures and Mechanical Properties of Mg-5Zn-xY-0.6Zr Alloys

Three as-cast and as-extruded Mg-5Zn-x Y-0.6Zr(x=5 wt%, 8 wt%, 11 wt%) alloys were prepared, and the effects of Y content on the microstructures and mechanical properties of the alloys were investigated. The results show that the investigated Mg-Zn-Y-Zr alloys mainly consist of a-Mg, X-Mg12 YZn and minor amount of W-Mg_3Y_2Zn_3 phases. The volume fraction of X-Mg_(12) YZn phase increases and that of W-Mg_3Y_2Zn_3 phase decreases with the rising of Y content in the alloys. The as-extruded Mg-5Zn-11Y-0.6Zr alloy owns the optimal ultimate tensile strength and yield strength of 429 and 351 MPa, respectively. Mg-5Zn-5Y-0.6Zr alloy owns the maximum elongation of 13.6%.     

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...