基于电化学性能的La-Mg-Ni系储氢合金的成分优化

以La-Mg-Ni系A2B7型储氢合金为研究对象,系统分析了合金A、B侧元素含量对其电化学性能的影响。对La1-m-n-y Pr m Nd n Mg y(Ni1-z Co z)x合金的容量和衰减速率进行了讨论。结果表明,合金容量随B/A值的增大先增大后减小,当x=3.5时,合金的容量最大,衰减速率最小;最佳的合金配比为La0.5Pr0.2Nd0.1Mg0.2(Ni0.8Co0.2)3.5。XRD分析表明,La1-m-n-y Pr m Nd n Mg y(Ni1-z Co z)x的合金主相结构均为Ce2Ni7型La2Ni7相。     

Zr/Mn元素替代及退火处理对汽车电池用储氢合金电化学性能的影响

采用真空感应熔炼的方法制备了(La,Mg)_1-xZr_x Ni_3.3-2xMn_2x(x=0、0.1、0.2)储氢合金，研究了Zr/Mn元素替代和退火处理对储氢合金相结构、显微形貌和电化学性能的影响。结果表明：Zr/Mn元素替代后储氢合金中出现了新相La Mg Ni₄相，退火处理后储氢合金中La Ni₅相和La Mg Ni₄相含量减小，(La,Mg)₂Ni₇相和(La,Mg)₅Ni₁₉相含量增加；当储氢合金中x值从0增加至0.2时，储氢合金电极的活化次数N_a逐渐减小、最大放电容量C_max逐渐降低，且相同x值时退火态储氢合金电极的C_max要高于铸态储氢合金电极。Zr/Mn元素替代会提高储氢合金电极的24 h荷电保持率、降低循环100次后的容量保持率，且退火后二者都会相对提高；铸态储氢合金电...     

La-Mg-Ni系贮氢合金相结构及电化学性能

采用感应熔炼法制备La0.75Mg0.25Ni3.4-xAl0.1Cox (x=0.0, 0.5, 1.0)贮氢合金,研究了合金元素Co对Ni部分替代对合金相结构及电化学性能的影响. 结果表明,合金由La2Ni7相、LaNi5相及LaMg2Ni9相组成. 随Co含量的增加,合金电极活化次数变化不大,最大放电容量、循环稳定性呈现先增后减的趋势. 合金的最大放电容量和循环保持率分别由x＝0时的316.92 mA.h/g和61.83%增加到x＝0.5时的340.31 mA.h/g和75.21%,而后减少到x＝1.0时的333.22 mA.h/g和66.70%. 而合金的高倍率放电性能降低,当放电电流密度为900 mA/g时,其倍率放电性能由62.49% (x=0)减小到53.68% (x=1.0). 合金电极的极限电流、贮氢合金电化学反应电阻逐渐增大,其高倍率放电性能的降低源于电极表面的电子迁移速率和氢在合金体相中扩散速率的共同作用.     

LaMg_2Ni_(9-x)Co_x(x=0.3～6.0)贮氢合金的制备及其性能研究

用共沉淀还原扩散法制备了不同化学计量比的LaMg2Ni9-xCox(x=0.3～6.0)稀土镁基贮氢电极合金。电化学测试结果表明:在x逐渐增大的过程中,合金的活化次数没有发生明显的变化,合金的放电容量逐渐减小,合金的循环稳定性逐渐增强。其中LaMg2Ni6.3Co2.7合金电极表现出的综合电化学性能较优。     

化学复合镀对LaMg2Ni6Mn3合金表面结构及电化学性能的影响

分别对AB3型贮氢合金(LaMg2Ni6Mn3)进行化学镀铜、化学镀镍及复合化学镀铜--镍合金.化学镀铜--镍合金后,最大放电容量由319 mA-h/g增大到390 mA-h/g,合金的容量衰减率从20%降至1%.X射线衍射结果显示,CuNi4O相和Mg2Ni3O相是导致合金最大放电容量增大以及循环稳定性增强的因素.扫...     

Ti替代La对AB_3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。     

汽车电池负极材料的制备与电化学性能研究

采用中频感应熔炼的方法制备了La_0.8-xCe_xMg_0.2Ni₃Co_0.6储氢合金,研究了不同Ce摩尔分数的退火态La_0.8-xCe_xMg_0.2Ni₃Co_0.6储氢合金的物相组成、微观结构和电化学性能。结果表明,La_0.8-xCe_xMg_0.2Ni₃Co_0.6储氢合金的主要物相都为（La, Mg）Ni₃、（La, Mg）₂Ni₇和LaNi₅相,随着x值从0增加至0.20,La_0.8-xCe_xMg_0.2Ni₃Co_0.6储氢合金的最大放电容量C_max和...     

球磨对Mg_(1.8)Al_(0.2)Ni_(0.8)Mn_(0.2)合金性能影响的研究

分别采用固相扩散法和随后球磨两步法制备Mg1.8A l0.2N i0.8Mn0.2型贮氢合金,研究了球磨对合金相的形成和其电化学性能的影响。SEM测试显示,球磨过程有利于非晶相的形成。充放电测试表明,在100 mA/g放电电流条件下,经过球磨后的合金最高放电容量可达110 mAh/g左右,而单纯固相扩散法合成的合金放电容量约为80mAh/g。循环寿命测试,球磨的样品经过50次循环其容量衰减到40%,非球磨样品经25次的循环即衰减到同样程度。合金的电化学性能的改善与球磨中结构变化所产生的晶体缺陷有关。     

稀土Cu/HZSM-5催化剂NH_3选择性催化还原法低温脱硝性能

采用浸渍法制备Re(x)Cu/HZSM-5(Re=La,Ce,Pr,Nd;x=0.5,1,2)系列催化剂。采用XRD和H_2-TPR等对催化剂进行表征,在微型固定床反应器中评价催化剂低温NH_3选择还原NO的催化活性。结果表明,Re(x)Cu/HZSM-5(Re=La,Ce,Pr,Nd;x=0.5,1,2)催化剂具有较好的低温NH_3选择还原NO催化活性,以La为助剂和添加质量分数1%的La(1)Cu/HZSM-5催化剂低温脱硝活性较好,T85和T95分别为153℃和164℃,活性温度窗口宽,(153~362)℃时,NO转化率超过95%。     

硼对非晶态LaMg11Zr+200%Ni储氢合金电化学性能的影响

以熔炼LaMg11Zr为母体合金,采用机械合金化法制备了非晶态LaMg11Zr+200%Ni+xB(x=0,2%,5%,10%)系列储氢合金,研究了B含量对合金结构和电化学性能的影响.结果表明:球磨20 h后,各合金均达到非晶态,B促进了非晶态合金的形成,提高了非晶态合金的热稳定性.合金电极均有良好的活化性能;随B含量的增加,合金电极的放电容量先增加后减少,LaMg11Zr+200%Ni+2%B合金电极达到最大放电容量614.2 mAh·g-1,比不含B合金电极提高了6.7%;添加B提高了合金电极的循环稳定性,充放电30周循环后合金电极的容量保持率由44.4%(x=0)增加到70.4%(x=10%);且添加B在一定程度上改善了合金电极的高倍率放电性能.     

Electrochemical and crystallographic characterization of Co-free hydrogen storage alloys for use in nickel–metal hydride batteries

Electrochemical and crystallographic characterization of Co-free hydrogen storage alloys containing Si and/or Fe was carried out. In the charge–discharge cycle test, the maximum discharge capacity of a Co-free MmNi_4.3Mn_0.4Al_0.3 (Mm=misch metal) alloy electrode was decreased by the partial substitution of Si and/or Fe for Ni, but the cycle performance was improved. The MmNi_3.6Mn_0.4Al_0.3Si_0.1Fe_0.6 electrode showed the most excellent cycle durability in this study. It was found by SEM, EPMA and XRD that Fe and Si contained in these alloys more or less suppressed the dissolution of Al and the lattice expansion with hydrogen absorption, leading to the long cycle life. This effect was strengthened by the simultaneous partial substitution of Si and Fe for Ni in the Co-free alloy.     

硼对非晶态LaMg11Zr＋200%Ni储氢合金电化学性能的影响

以熔炼LaMg₁₁Zr为母体合金,采用机械合金化法制备了非晶态LaMg₁₁Zr＋200%Ni+xB(x=0,2%,5%,10%)系列储氢合金,研究了B含量对合金结构和电化学性能的影响。结果表明：球磨20 h后,各合金均达到非晶态,B促进了非晶态合金的形成,提高了非晶态合金的热稳定性。合金电极均有良好的活化性能;随B含量的增加,合金电极的放电容量先增加后减少,LaMg₁₁Zr＋200%Ni+2%B合金电极达到最大放电容量614.2 mAh.g^-1,比不含B合金电极提高了67%;添加B提高了合金电极的循环稳定性,充放电30周循环后合金电极的容量保持率由44.4%(x=0)增加到70.4%(x=10%);且添加B在一定程度上改善了合金电极的高倍率放电性能。     

汽车电池负极镁基合金Mg-Ni-Y-Gd的组织与性能

针对目前汽车电池存在续航不足、放电不稳定等问题,采用不同的球磨工艺制备了MgNi-Y-Gd和Mg2Ni汽车电池负极镁基合金,并对其组织、放电性能和耐腐蚀性能进行了测试与分析。结果表明:在500 r/min下球磨48 h后两种合金都是非晶合金。与Mg2Ni相比,Mg-Ni-YGd合金腐蚀电位正移53 mV,充放电循环25次后放电容量减小13.5%,合金的耐腐蚀性能和放电性能得到明显提高。     

Electrode stabilities of copper-containing misch metal-nickel-based hydride forming alloys

Electrochemical charge-discharge cycling measurements were conducted on electrode samples prepared from alloy powders of a series of Cu-containing Ce- and La-rich misch metal (Mm and Ml, respectively)-Ni-based stoichiometric multicomponent alloys. A severe decrease in the electrochemical capacity was observed for Mm-Ni-Al electrodes, which was believed to be related to the deterioration of electrical contact within the electrodes, in addition to the decomposition of the active materials. Although the addition of cobalt powders to these electrodes improved the electrical contact within the electrodes, it had no effect on retarding the decomposition of the active materials. The substitution of copper into the Mm-Ni-Al composition improved the stability of this electrode material, but brought about a decrease in its electrochemical capacity. As a compromise, partial substitutions of copper for cobalt in Mm-Ni-Co-Al, Mm-Ni-Co-Mn-Al as well as Ml-Ni-Co-Al alloys were proved to be possible without remarkable changes in electrode properties, but too much of this substitution brought about decreases in material stability, which was observed to be accompanied by an increase in tendency of the materials to pulverize during electrochemical cycling.     

电动汽车用La-Fe-B储氢合金的制备与电化学性能研究

研究了石墨烯含量对储氢合金物相组成和电化学性能的影响。结果表明,不同石墨烯含量储氢合金都主要由La₃Ni₁₃B₂、LaNi₅和（Fe,Ni）相组成,La₃Ni₁₃B₂和（Fe,Ni）相晶胞体积会随着石墨烯含量增加而增大,LaNi₅相晶胞体积会随着石墨烯含量增加而减小。当石墨烯质量分数从0%增加至6%时,储氢合金的最大放电容量先增加后减小,在石墨烯质量分数为4%时取得储氢合金放电容量最大值（288.5 mA·h/g）,且当循环周期为100次时,石墨烯质量分数为4%和6%的储氢合金的放电容量仍然高于未添加石墨烯的储氢合金。相同温度下,添加石墨烯的储氢合金的放电容量都高于未添加石墨烯的储氢合金,且石墨烯质量分数为4%的储氢合金具有最大放电容量。随着石墨烯质量分数从0%增加至6%,储氢合金的电荷转移电阻先减小后增大、电流密度和扩散系数先增大后减小,在石墨烯质量分数为4%时取得电荷转移电阻最小值、电流密度和扩散系数最大值,适宜的石墨烯添加量为4%。     

Zr_(0.9)Ti_(0.1)(Ni,Co,Mn,V)_(2+α)贮氢合金的制备过程对其性能的影响

测定了Zr_(0.9)Ti_(0.1)-Ni,Co,Mn,V)2+( 贮氢合金在铸态、快淬态及快淬合金经不同退火温度处理后的压力(组成(温度曲线，计算了它们的焓变值，测试了其电化学容量. 结果表明：快淬后的贮氢合金随退火温度的增加，焓变值和放电容量也增加. 在1173 K温度下退火处理的贮氢合金，其放电容量(379 mA(h/g)较铸态合金好，但它的活化性能不如铸态合金.     

Electrodeposition and lithium storage performance of three-dimensional porous reticular Sn-Ni alloy electrodes

Three-dimensional (3D) porous materials of Sn-Ni alloy with reticular structure were prepared by electroplating using copper foam as current collector. The structure and electrochemical performance of the electroplated 3D porous Sn-Ni alloys were investigated in detail. Experimental results illustrated that the 3D porous Sn-Ni alloy consists of mainly Ni₃Sn₄ phase with a hexagonal structure. Galvonostatic charging/discharging of annealed 3D porous Sn-Ni alloy confirmed its excellent performances: at 50th charge-discharge cycle, the discharge specific capacity is 505 mAh g⁻¹ and the corresponding charge (delithiation) specific capacity is 501 mAh g⁻¹, yielding columbic efficiency as high as 99%. It has revealed that the porous structure of the alloy can restrain the pulverization of electrode in charge/discharge cycles, and accommodate partly the volume expansion and phase transition, resulting in a significant improvement of cycle life of the Sn-Ni electrode.     

A study on structure and electrochemical properties of (La, Ce, Pr, Nd)2MgNi9 hydrogen storage electrode alloys

(La, Ce, Pr, Nd)₂MgNi₉ hydrogen storage alloys were prepared through induction melting followed by a long annealing treatment. The structure and electrochemical properties of annealed alloys have been investigated by orthogonal design experiments. Both the individual effects of each substituting element and their interaction in alloys were studied systemically. It has been shown that the structure of main phase in alloys belongs to PuNi₃-type with a space group R-3m. Substituting rare-earth elements have a significant effect on both the phase structure of alloys and microstructure. The anisotropic change in the crystal structure of alloys can cause the acceleration of pulverization of alloy particles and result in the deterioration of the cyclic stability of alloy electrodes. Misch metals can raise the plateau pressure of hydrogen absorption/desorption. The discharge capacity of alloy ranges from 342.97 to 380.68 mAh g⁻¹ depending on the sort and content of substituting elements. Both cerium and neodymium can obviously reduce the discharge capacity of alloy electrodes. When compared to the La₂MgNi₉ alloy electrode, mish metals can significantly improve the high rate dischargeability of alloy electrodes. The improvement of the kinetic characteristic of alloy electrodes mainly results from the increase of the hydrogen diffusion rate in alloy bulk.     

四元复合氧化物La_(0.5)Sr_(0.5)Ni_(0.5)Cu_(0.5)O_3的抗硫性能

以SO2 为毒物 ,采用脉冲中毒方法 ,再以CO氧化反应为探针 ,对三元复合氧化物催化剂La0 .5Sr0 .5NiO3 与La0 .5Sr0 .5CuO3 以及四元复合氧化物催化剂La0 .5Sr0 .5Ni0 .5Cu0 .5O3 等三种催化剂样品的抗硫毒能力、失活曲线、中毒催化剂的再生性能以及毒物残留形态等进行了全面考察和对比分析。实验结果表明四元复合氧化物催化剂La0 .5Sr0 .5Ni0 .5Cu0 .5O3 在SO2 毒物含量是 1 2 2×10 -2 mmol时 ,特别是在高温 (≥ 30 0℃ )条件下 ,具有优异的抗硫性能