Microstructural evolution and performance of hydrogen storage and electrochemistry of Co-added La0.75Mg0.25Ni3.5−xCox (x = 0, 0.2, 0.5 at%) alloys

Microstructure, hydrogen storage and electrochemical performances of Co-added La_(0.75)Mg_(0.25)Ni_(3.5_x)Co_x(x = 0,0.2, 0.5 at%) alloys are studied. XRD and rietveld refinement results suggest that the samples are mainly composed of(LaMg)Ni_3,(LaMg)_2Ni_7 and LaNi_5 phases, Co substitution for Ni changes the phase abundance,but not the phase composition. With the rising of Co content, the amount of(LaMg)_2 Ni_7 phase decreases, but the amount of LaNi_5 phase increases, while the amount of(LaMg)Ni_3 phase firstly increases and then decreases.The alloys reversibly absorb and desorb hydrogen at 298 K smoothly. When Co content is 0.2 at%, the hydrogen absorption capacity reaches the maximum value of 1.14 H/M, and the absorption capacities reach 1.09 H/M and 1.03 H/M in the first minute at 298 K and 323 K, respectively. Electrochemical performance measurement results show that La_(0.75)Mg_(0.25)Ni_(3.5-x)Co_x alloys are completely activated within 2 cycles, and the cyclic stability of La_(0.75)Mg_(0.25)Ni_(3.3)Co_(0.2) alloy approaches 63.7% after 100 charge/discharge cycles, which is higher than that(S_(100) = 60%) of La_(0.75)Mg_(0.25)Ni_(3.0)Co_(0.5) alloy. Thus, the La_(0.75)Mg_(0.25)Ni_(3.3)Co_(0.2) alloy exhibits optimum comprehensive properties of hydrogen storage and electrochemistry.     

Effect of rolling geometry on the mechanical properties,microstructure and recrystallization texture of Al–Mg–Si alloys

The effect of rolling geometry on mechanical properties, microstructure, and recrystallization texture of Al–Mg–Si alloys was studied by means of tensile tests, microstructural observations, and electron backscatter diffraction measurements. The results reveal that the elongation and the average plasticity strain ratio(r) values of the T4P(pre-aging plus natural aging)-treated alloy sheet with a rolling geometry value between 1 and 3 are somewhat higher than those of the T4P-treated sheet with a rolling geometry value between 3 and 6. The deformation and recrystallization microstructures of the sheet with a rolling geometry value between 1 and 3 are more uniform than those of the sheet with a rolling geometry value between 3 and 6. The former also possesses somewhat higher surface quality. H {001}110 and Goss {110}001 orientations are the main recrystallization texture components for the former case, whereas the latter case only includes H{001}110 orientation. Texture gradients are present in the two alloy sheets. Shear texture component F on the surface of the sheet with a rolling geometry value between 3 and 6 and its higher texture gradients have revealed that non-uniform deformation occurred during cold rolling. The effects of texture on the yield strength and r value were also discussed.     

Effect of Sr on microstructure and aging behavior of Mg–14Li alloys

The as-cast and as-extruded Mg–14 wt%Li–x Sr ( x=0.14, 0.19, 0.39 wt%) alloys were,respectively, prepared through a simple alloying process and hot extrusion. The effects of Sr addition on microstructure and aging behavior of the Mg–14 wt%Li–xSr alloys were studied. The results indicated that β(Li) and Mg2Sr were the two primary phases in the microstructures of both as-cast and as-extruded Mg–14 wt%Li–xSr alloys. Interestingly, with the increase of Sr content from 0.14 wt% to 0.39 wt%, the grain sizes of the as-cast and as-extruded Mg–14 wt%Li–xSr alloys markedly decreased from 5000mm and 38mm to 330 mm and 22mm respectively, while no obvious changes of the micro-hardness and microstructure of the as-extruded alloys were observed during the aging treatment.     

Effect of Al on microstructure and mechanical properties of as-extruded Mg–1Mn alloy sheet

The effect of Al addition on microstructure and mechanical properties of hot extruded Mg–1 Mn alloy sheet was investigated. The results revealed that the dynamic recrystallization was promoted by increasing Al content. The ultimate tensile strength and yield strength of the alloy increased with the increase of Al content. The Mg–9 Al–1 Mn alloy exhibited the highest strength, with tensile strength of 308 MPa, 307 MPa, 319 MPa, yield strength of 199 MPa, 207 MPa, 220 MPa and the elongation of 20.9%, 20.1%, 19.2% in 0°, 45°, 90°, respectively.The high strength was mainly attributed to the formation of fine dynamically recrystallized grains and large amounts of the second phase. The strengthening mechanism of the alloys was explained.     

Effect of Mn content on the microstructure and mechanical properties of Mg–6Li–4Zn-xMn alloys

The as-cast Mg–6Li–4Zn-x Mn alloys were prepared and extruded at 280℃ with an extrusion ratio of 25:1. The effects of Mn content on the microstructure and mechanical properties of Mg–6Li–4Zn-x Mn alloys were investigated in this study. The XRD results show that Mg–6Li–4Zn–x Mn alloys consisted of α-Mg(hcp) + β-Li(bcc)duplex structured matrix, Mg Li₂Zn and Mn phases. The grains of the extruded Mg–6Li–4Zn–x Mn alloys were refined by dynamic recrystallization during the extrusion process...     

Electrochemical hydrogen storage properties of Mg100−xNix produced by hydriding combustion synthesis and mechanical milling

In this work, Mg-based hydrogen storage composites with an initial 100-x: x (x=25, 32.3, 50, 66.7) of Mg:Ni molar ratio were prepared by HCS+MM and their phase compositions and electrochemical performances were investigated in detail. The results show that the composites with desirable constituents can be achieved by adjusting the molar ratio of the starting materials in the HCS process. Particularly, the HCS product of Mg67.7Ni32.3 consists of the principal phase Mg2NiH4 and minor phase Mg2NiH0.3. The dominate phase varies from Mg2NiH0.3 and MgH2 for the Mg enriched sample (x<32.3) to MgNi2 and Ni for the Ni enriched sample (x>32.3). The MM modification not only brings about grain refinement of the alloys, but also leads to phase transformation of part Mg2NiH4 to Mg2NiH0.3 in the Mg67.7Ni32.3 sample. Electrochemical tests indicate that each sample can reach its maximum discharge capacity at the first cycle. Mg67.7Ni32.3 displays the highest discharge capacity as well as a superior electrochemical kinetics owing to its excellent H atom diffusion ability and lower charge-transfer resistance. The Mg67.7Ni32.3 provides the most optimized Mg/Ni atomic ratio considering the comprehensive electrochemical properties of all samples.     

Microstructures and mechanical properties of as-extruded Mg–5Sn–1Zn–xAl(x=1, 3 and 5) alloys

As-extruded Mg–5Sn–1Zn–xAl alloys(x=1, 3, and 5) were fabricated by hot extrusion. The experimental results revealed that the yield strength of alloys initially decreased and then increased with the increase of Al content. These changes were mainly attributed to the difference in crystallographic texture and volume fractions of second phases. The ultimate tensile strength, yield strength, and elongation of the alloys were greater than 310 MPa, 227 MPa, and 11%, respectively. The strain hardening ability of the alloys was also discussed.     

Effect of Zn addition on microstructure and mechanical properties of an Al–Mg–Si alloy

In the present work, an Al–0.66Mg–0.85Si–0.2Cu alloy with Zn addition was investigated by electron back scattering diffraction(EBSD), high resolution electron microscopy(HREM), tensile and Erichsen tests. The mechanical properties of the alloy after pre-aging met the standards of sheet forming. After paint baking, the yield strength of the alloy was improved apparently. GP(Ⅱ) zones and η’phases were formed during aging process due to Zn addition. With the precipitation of GP zones, β″ phases, GP(Ⅱ) zones and η’phases, the alloys displayed excellent mechanical properties.     

Effect of ECAP temperature on microstructure and mechanical properties of Al–Zn–Mg–Cu alloy

The effect of equal channel angular pressing(ECAP) at different temperatures(room temperature, 120,150 and 180 °C) on microstructure and mechanical properties of Al-7075 solid solution alloy was investigated. Microstructure of the specimens was examined using orientation imaging microscopy,transmission electron microscopy as well as X-ray diffractometer, and mechanical properties were measured by Vickers microhardness and tensile tests. Microstructural investigations showed that after3 or 4 passes of ECAP, fi ne grains with average grain sizes in range of 300–1000 nm could be obtained at different ECAP temperatures. Increasing ECAP temperature from 120 to 180 °C caused a decrease in mechanical properties as a result of increasing grains and precipitates sizes, decreasing fraction of high angle boundaries and also transformation of η′ into η phase, while increasing ECAP temperature from RT to 120 °C leads to an increase in mechanical properties due to the formation of small η′ precipitates. So it can be concluded that ECAP process at 120 °C is the optimum process for attaining maximum mechanical properties. Quantitative estimates of various strengthening mechanisms revealed that the improvement of mechanical properties was mainly attributed to grain re fi nement strengthening, precipitation strengthening and dislocation strengthening.     

Effect of particle size distribution on the microstructure,texture, and mechanical properties of Al–Mg–Si–Cu alloy

The effect of particle size distribution on the microstructure, texture, and mechanical properties of Al–Mg–Si–Cu alloy was investigated on the basis of the mechanical properties, microstructure, and texture of the alloy. The results show that the particle size distribution influences the microstructure and the final mechanical properties but only slightly influences the recrystallization texture. After the pre-aging treatment and natural aging treatment (T4P treatment), in contrast to the sheet with a uniform particle size distribution, the sheet with a bimodal particle size distribution of large constituent particles and small dispersoids exhibits higher strength and a somewhat lower plastic strain ratio (r) and strain hardening exponent (n). After solution treatment, the sheet with a bimodal particle size distribution of large constituent particles and small dispersoids possesses a finer and slightly elongated grain structure compared with the sheet with a uniform particle size distribution. Additionally, they possess almost identical weak recrystallization textures, and their textures are dominated by CubeND {001}<310> and P {011}<122> orientations.     

Ml0.75Mg0.25Ni3.5-x Alx合金储氢性能及电化学性能研究

在Ar气保护下,采用悬浮熔炼方法制备Ml0.75 Mg0.25 Ni3.5 -xAlx(x=0.05 ～0.25)合金,系统研究Al部分取代Ni对合金的相结构、吸放氢性能和电化学性能的影响.结果表明,合金的相结构主要由具有六方CaCu5结构的(La,Pr) Ni5相、(La,Pr) Mg2Ni9相和(La,Nd)2 N...     

La0.7Mg0.3-xTixNi2.8Co0.3(x=0.03,0.06,0.09,0.12)合金的储氢与电化学性能研究

用高频感应熔炼方法制备了La0.7Mg0.3-xTixNi2.8Co0.3(x=0.03,0.06,0.09,0.12)系列合金,并对其储氢和电化学性能进行测试.结果表明x=0.06时,合金储氢性能最好,气态储氢容量达1.2wt%,放电容量和比容量分别为336 mA.h.g-1,70.0%.     

Mg2Ni+x0.5 wt% V2O5+y0.5 wt Ni(x,y=0,1)复合体系的贮氢和电化学性能研究

用球磨方法制备Mg2Ni x0.5 wt%V2O5 y0.5 wt Ni(x,y=0,1)复合贮氢合金,并进行气态吸放氢变温动力学与电化学充放电实验.结果表明,x,y=1时体系的气态吸放氢和放电容量效果最好,多元复合的放电容量超过单一化合物的放电容量的总和.     

La0.7Mg0.3-xCaxNi2.5Co0.5(x=0～0.15)储氢合金的放电容量衰退机理研究

采用感应熔炼结合粉末烧结两步法制备了La_(0.7)Mg_(0.3-x)Ca_xNi_(2.5)Co_(0.5)(x=0～0.15)储氢合金,并对合金的放电容量衰退机理进行了研究.研究结果显示随着Ca含量的增加,合金的相结构没有发生明显变化,只是晶胞参数逐渐增大,即Ca主要替代了超晶格结构AB2结构单元中的Mg,但在AB5结构单元中少量的Ca恰恰对合金的放电容量产生了重要的影响.Ca在AB2和AB5两种结构单元中的存在会降低储氢过程中晶胞内部的膨胀应力,Ca的溶解能够抑制Mg的腐蚀,生成微溶于水的腐蚀产物,并提高了合金表面具有催化活性的Ni含量,改善了合金的循环寿命.较高的Ca含量会严重破坏合金的相结构,生成过量的腐蚀产物因不能完全溶于水而在合金表面形成包覆层,阻碍了电极反应,造成合金循环过程中放电容量的急剧下降.     

La3-xYxMgNi14(x=0～2)贮氢合金的相结构与电化学性能研究

系统研究了La3-xYxMgNi14(x=0,1.0,1.5,2.0)贮氢合金的相结构和电化学性能.结构分析表明,合金均由Gd2Co7和Ce2Ni7型结构相组成.随Y含量值x的增加,Gd2Co7型相的丰度增加,Ce2Ni7型相的丰度减少.合金各相的晶胞参数(a,c)和晶胞体积(V)均随x的增加而线性减小.电化学研究表明,随着Y含量的增加,合金电极最大放电容量减小,活化性能显著降低.合金随x的增加,HRD值减小与合金电极电催化活性及氢在合金相中的扩散速率的减小有关.     

稀土元素R对储氢合金(LaRMg)(NiCoAlZn)3.5相结构和电化学性能的影响

以(LaRMg)(NiCoAlZn)3.5(R=La、Ce、Pr、Nd、Gd、Y和Sc)合金为研究对象,研究稀土元素R部分替代La后对合金相结构和相组成及电化学性能的影响.XRD和EPMA方法分析结果表明,合金(LaRMg)(NiCoAlZn)3.5退火组织主要由Ce2Ni7型相(或Gd2Co7型)、PuNi3型相和CaCu5型相组成;Ce、Pr和Nd元素的替代对合金相组成没有明显影响,而Gd元素替代使合金中CaCu5型相明显减少,Ce2Ni7型(或Gd2Co7型)相显著增加,其相丰度达到79.03%;Y和Sc元素替代时合金中Gd2Co7型相基本消失.电化学测试和分析表明, 稀土元素R替代La后对合金电极活化性能影响不大,其中Nd、Gd、Y和Sc部分替代La在一定程度上提高合金的最大放电容量,而Gd元素替代时合金电极容量最高达到343.1 mAh/g;Gd和Nd元素部分替代La使合金电极的循环稳定性得到明显提高,S100分别达到95.3%和93.0%.此外,Sc部分替代La能有效改善合金电极的高倍率放电性能.     

Microstructure characterization and hydrogen storage properties study of Mg2Ni0.92M0.08 (M = Ti, V, Fe or Si) alloys

In the present study Mg_2Ni-type compounds alloyed independently with Ti,V,Fe and Si were successfully prepared by wet-milling followed by sintering.Although these alloyed Mg_2Ni compounds exhibited a similar hydrogen storage mechanism as that of pure Mg_2Ni,the dissolution of Ti,V or Fe into the Mg_2NiH_4lattice had a considerable catalytic effect on hydrogen desorption from additional MgH_2.The further structure investigations clearly indicated that the substitution of Ti for Ni could suppress the formation of the micro-twined low-temperature phase(LT2)and promote the formation of the high-temperature phase(HT),thus resulting in remarkably improved hydrogen desorption kinetics for the Mg_2Ni_(0.92)Ti_(0.08)–H system.     

Mg-50wt.%Ti_(1-x)C(x=0.1,0.2,0.3,0.4)合金的贮氢性能研究

采用机械合金化方法制备Mg-50wt.%Ti1-xCx(x=0.1,0.2,0.3,0.4)贮氢合金.x-射线衍射(XRD)分析结果表明,合金主要由Mg、Ti、c以及二元合金相Ti2C0.06和Mg2C3组成,随着球磨时间增加,合金的非晶化程度提高.压强-成分-温度(Pcr)测试结果显示,Mg-50wt.%Ti1-xC(x=0.1,0.2,0.3,0.4)合金的贮氢量分别为2.96、2.95、2.76、2.6wt.%;随着碳含量的增加,样品吸氢量逐渐减少,放氢温度和平台压也随之下降;适当增加球磨时间可降低吸放氢温度.     

Ti替代La对AB3型储氢合金的结构与电化学性能的影响

研究(La1-xTix)2MgNi8.25Co0.75(x=0、0.1、0.2)合金的微观结构与电化学性能。相测试结果显示:所有合金都是由(La,Mg)Ni3和LaNi52个主相所构成的,晶胞参数随着Ti的替代而逐渐减小,这是因为Ti的共价键半径(0.132 nm)小于La(0.169 nm)所引起的。电化学测试结果表明:所有的合金电极经过4次活化后都能够达到最大放电容量,且放电容量随着Ti含量的增加而减少,从x=0时的384.6 mAh/g降低到x=0.2时的321.9 mAh/g,合金电极的循环寿命则从x=0时的53.1%提高到x=0.2时的67.8%,合金在1 200 mA/g时的高倍率放电性能先从x=0时的59.3%升高到x=0.1时的66.5%,然后又降低到x=0.2时的63.1%。此外,电化学动力学也显示出先增大后减小的特点。造成以上电化学性能变化的原因是Ti的加入一方面起到了脱氢催化的作用,另一方面使合金表面形成了致密氧化层,虽然阻止了合金进一步的腐蚀,但也降低了合金电极的动力学性能。