电感耦合等离子体质谱法测定镧镁合金中稀土杂质

采用硝酸溶解样品,建立了电感耦合等离子体质谱法（ICP-MS）测定镧镁合金中稀土杂质的含量.选择合适的测定同位素以及选用干扰元素校正方程克服了质谱干扰.对仪器工作条件进行了优化,确定功率为1 100 W,载气流量为0.80 L/min.讨论了测定条件对结果的影响,确定测定介质为1％硝酸,内标元素为Cs,基体浓度小于0.3 mg/mL.方法测定下限为0.006 9～0.046 ng/mL.采用方法对实际样品进行测定,回收率为98％～102％.与电感耦合等离子体发射光谱法（ICP AES）进行方法对照,两种方法测定结果基本一致,相对标准偏差（RSD,n=6）在1.7％～4.5％之间.

放电等离子烧结制备镧镁镍贮氢合金

为了改善镧镁镍贮氢合金的循环稳定性,以La0.78Mg0.22Ni3.70合金为研究对象探索放电等离子烧结适宜温度。采用扫描电镜(SEM)、X射线衍射(XRD)分析了合金的断口形貌及相结构,电池测试仪测试了合金的电化学性能。结果表明,合金的烧结过程含有膨胀—收缩阶段,收缩阶段相对较长。随烧结温度升高,合金收缩引起的位移增加,合金断口先致密后蓬松,含有LaNi5、(La,Mg)2Ni7主相以及LaNi2.28残余相。与其它温度烧结合金相比,950℃烧结合金具有较高的放电容量和循环稳定性。

电沉积制备La-Mg-Ni贮氢合金薄膜及其性能的研究

采用恒电流沉积方法在水溶液中沉积出LaMgNi4合金薄膜。利用循环伏安、模拟电池充放电循环、扫描电镜(SEM)以及X射线衍射(XRD)等方法研究了电沉积合金薄膜的电化学性能和表面形貌及结构。结果表明,该合金薄膜作为贮氢电极具有较好的电化学性能,其电化学活性高,活化性能好,首次充放电比容量达398mAh/g。

Influences of stoichiometric ratio B/A on structures and electrochemical behaviors of La_(0.75)Mg_(0.25)Ni_(3.5)M_x (M=Ni,Co;x=0-0.6) hydrogen storage alloys

In order to investigate the influences of the stoichiometric ratio of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structures and electrochemical performances of the AB3.5-4.1-type electrode alloys, the La-Mg-Ni-Co system La0.75Mg0.25Ni3.5Mx (M=Ni, Co; x= 0, 0.2, 0.4, 0.6) alloys were prepared by induction melting in a helium atmosphere. The structures and electrochemical performances of the alloys were systemically measured. The results show that the structures and electrochemical performances of the alloys are closely relevant to the B/A ratio. All the alloys exhibit a multiphase structure, including two major phases, (La, Mg)2Ni7 and LaNi5, and a residual phase LaNi2, and with rising ratio B/A, the (La,Mg)2Ni7 phase decreases and the LaNi5 phase increases significantly. When ratio B/A=3.7, the alloys obtain the maximum discharge capacities. The high rate discharge(HRD) capability of the alloy (M=Ni) monotonously rises with growing B/A ratio, but that of the alloy (M=Co) first mounts up then declines. The cycle stability of the alloy (M=Co) monotonously increases with rising B/A ratio, but it first decreases slightly then increases for the alloy (M=Ni). The discharge potential of the alloy (M=Ni) declines with increasing B/A ratio (x>0.2), but for the alloy (M=Co), the result is contrary. The substitution of Co for Ni significantly ameliorates the electrochemical performances. For a fixed ratio B/A=3.7, the Co substitution enhances the discharge capacity from 365.7 to 401.8 mA·h/g, the capacity retention ratio (S100) after 100 charging-discharging cycles from 50.32% to 53.26% and the HRD from 88.65% to 90.69%.

Influences of heat treatment on electrochemical characteristics of La_(0.75)Mg_(0.25)Ni_(2.8)Co_(0.5) hydrogen storage electrode alloy

The influences of annealing treatment on the electrochemical and structural properties of La 0.75Mg 0.25- Ni 2.8Co 0.5 hydrogen storage alloy were investigated by means of electrochemical studies and X-ray diffraction(XRD) analyses. The XRD results reveal that the peak width gets narrower with increasing annealing temperature, which can be ascribed to the structural change and more homogeneous composition after being annealed. Electrochemical studies show that the discharge capacity and the cycle stability of the alloy electrodes increase after being annealed. The maximum discharge capacity, exchange current density J 0 and limiting current density J L of the as-cast alloy are 388 mA·h/g, 340.5 mA/g and 3 068 mA/g, respectively, and they are increased to 400 mA·h/g, 372.1 mA/g and 3 399 mA/g for the alloy annealed at 1 123 K for 8 h, respectively. Meanwhile, as the discharge current density is 1 250 mA/g, the high rate dischargeability(HRD) increases from 77.4% for the as-cast alloy to 83.3% for the alloy annealed at 1 123 K.

Cycle stability of La_(0.7)Mg_(0.3)Ni_(2.55-x)Co_(0.45)Cu_x(x=0-0.4) electrode alloys

The La0.7Mg0.3Ni2.55-xCo0.45Cux (x=0, 0.1, 0.2, 0.3, 0.4) electrode alloys were prepared by casting and rapid quenching. Ni in the alloy was partially substituted by Cu in order to improve the cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy. The effects of substituting Ni with Cu on the microstructures and cycle stability of the alloys were investigated in detail. The results obtained by XRD, SEM and TEM show that the substitution of Cu for Ni is favourable for the formation of an amorphous in the as-quenched alloy, and this leads to an obvious refinement of the as-quenched alloy grains and a growth of the lattice constants and cell volumes of the as-cast and quenched alloys. The results obtained by the electrochemical measurement indicate that the cycle stability of the alloys significantly rises with the incremental variety of Cu content. When Cu content changes from 0 to 0.4, the cycle lives of the as-cast and quenched (30 m/s) alloys are enhanced from 72 to 88 cycles and from 100 to 121 cycles, respectively.

Influence of addition of Cu(OH)_2 to KOH alkaline electrolyte on electrochemical properties of La_2Mg_(0.9)Al_(0.1)Ni_(7.5)Co_(1.5) hydrogen storage alloy electrode

The influence of the addition of Cu(OH)2 to 6 mol/L KOH alkaline electrolyte on the electrochemical properties of La2Mg0.9Al0.1Ni7.5Co1.5 hydrogen storage alloy electrode was investigated by electron probe X-ray microanalysis(EPMA),X-ray diffraction(XRD) and electrochemical measurements. EPMA micrographs and XRD patterns show that the surface of the hydride electrode is plated by metal copper film. The thickness and compactness of Cu film increase with the increment of charge-discharge cycle number. The copper film of the hydride electrode surface can keep the hydrogen storage alloy particle in the electrode interior from oxidizing availably. The addition of Cu(OH)2 to alkaline electrolyte lowers the activation property and the high rate dischargeability of the La2Mg0.9Al0.1Ni7.5Co1.5 hydride electrode,but has no negative effect on the maximum discharge capacity of the hydride electrode. Moreover,it is effective to improve the cyclic stability of the hydride electrode utilizing electrodeposit Cu film on the La2Mg0.9Al0.1Ni7.5Co1.5 hydride electrodes surface.

化学镀镍对LaMgNi_(3.7)Co_(0.3)储氢合金电化学性能的影响

在LaMgNi3.7Co0.3储氢合金粉末表面进行化学镀镍处理。镀覆镍的合金粉末与镍粉混合后涂于泡沫镍上制成电极。当镀液中Ni2+为40 g/L、温度为50°C、镀液pH为8.0、反应时间为30 min时,合金电极在6 mol/L KOH电解液中的最大放电容量和循环稳定性都有显著提高,合金电极的交换电流密度增大,极化电阻降低,其动力学性能增强。