Effect of CoO Addition on Electrochemical Properties of La0.7Mg0.3 （Ni0. 85 Co0. 15 ） 3.5 Hydrogen- Storage Alloy

In order to improve the cycling stability of La-Mg-Ni-Co hydrogen storage alloys, the La0.7Mg0.3 （Ni0.85Co0.15）3.5 alloy was prepared by inductive melting under argon atmosphere. The effect of additive CoO on electrochemical properties of La0.7Mg0.3（Ni0.85 Co0.15）3.5 alloy, which is used as an electrode material was studied. When the addition of CoO is 5 %, both the discharge capacity at high-, low- and room-tem- perature and charge-discharge cycling stability at room temperature can be significantly improved. Electro- chemical measurements and X-ray diffraction （XRD） analyses suggest that CoO improves the electrochemical properties of the La0.7Mg0.3（Ni0.85Co0.15）3.5 alloy by promoting the electrochemical reaction of another phase in the alloy and by self electrochemical reversible reaction occurring during the charge-discharge process.     

Effect of Rapid Quenching on Microstructures and Electrochemical Performances of La2Mg（Ni0.85Co0.15）9M0.1 （M = B, Cr） Hydrogen Storage Alloys

The La-Mg-Ni-system （PuNi3-type） La2Mg （Ni0.85 Co0.15 ）9M0.1 （ M = B, Cr） hydrogen storage etectrode alloys were prepared by casting and rapid quenching. The electrochemical performances and microstructures of the as-cast and quenched alloys were determined and measured. The effects of rapid quenching on the microstructures and electrochemical properties of the alloys were investigated in detail. The obtained results show that the alloys are composed of the （La, Mg） Ni3 phase （PuNi3-type structure） and the LaNi5 phase, as well as the small amount of the LaNi2 phase. A trace of the Ni2B phase exists in the as-cast alloy containing boron, and the Ni2B phase in the alloy nearly disappears after rapid quenching. The relative amount of each phase in the alloys depends on the quenching rate. The rapid quenching technique can greatly improve the electrochemical performance of the alloy, and the effect of rapid quenching on the activation performances of the alloys is minor. Rapid quenching enhances the cycle stability of the alloy, and the cycle life of the alloy increases with the increase of the quenching rate.     

Electrochemical properties of cobalt-free La0.80Mg0.20Ni2.85Al0.11M0.53 （M=Ni, Si, Cr, Cu, Fe） alloys

In order to investigate the effect of different B-site additions on phase structure and electrochemical properties of cobalt-free La-Mg-Ni based alloys, La0.80Mg0.20Ni2.85Al0.11M0.53 (M=Ni, Si, Cr, Cu, Fe) hydrogen storage alloys were prepared and studied systemati-cally. X-ray powder diffraction showed that the alloys consisted mainly of LaNi3 phase and LaNi5 phase except that Cr addition caused a minor Cr phase. Electrochemical testing indicated that alloys with additional Ni, Cr, Cu or Fe were activated within only 1-2 cycles, while that with Si addition needed 4 cycles. Adding Si, Cu and Fe increased cycling stability of La-Mg-Ni based alloys. However, maximum discharge capacity decreased from 362 mAh/g to 215 mAh/g in the order of Ni>Fe>Cu>Cr>Si. In addition, electrochemical kinetics of alloy electrodes was also researched by measuring high rate discharge ability (HRD), hydrogen diffusion coefficient (D) and limiting current density (IL).     

Effect of Rare Earth Metals on Structure and Properties of Electroless Co-B Alloy Coating

The effect of rare earth metals cerium, lanthanum and yttrium on chemical composition, structure and properties of electroless Co-B alloy coating was studied. By plasma transmitting spectrograph, electron energy spectrometer, X-ray diffractometter, miero-hardometer and vibratory- sample magnetometer the chemical constitution,structure and properties of the alloy coatings were analyzed and inspected. The results show that with a tiny quantity of rare earth metal added into Co-B alloy coating, the content of boron is decreased in the alloy coatings, and the kinds of rare earth metal have enormous effect on the structure and properties of electroless Co-B alloy coating. At the same time electroless Co-B alloy with amorphous structure is transformed to electroless Co-B-RE alloy with microcrystalline or crystalline structure. In this way microhardness of the coatings is increased remarkably. Cerium and lanthanum would also increase the saturated magnetic intensity and decrease coercitive force of the coating. So soft magnetization of the coatings would be improved.     

Phase Structure and Electrochemical Characteristics of Ml（Ni3.55Co0.75Mn0.40Al0.30）5x （x=0.88, 0.92, 0.96, 1.00） Hydrogen Storage Alloys

The phase structure and electrochemical characteristics of Ml （（Ni3.55Co0.75Mn0.40Al0.30）sx （ x = 0.88, 0.92, 0.96, 1.00） hydrogen storage alloys were studied. The effect of the stoichiometric ratio on the phase structure and electrochemical characteristics was analyzed. The results of XRD reveal that all the alloys consist mainly of LaNi5 phase with the hexagonal CaCu5 structure. But a few of the diffraction peaks of La2Ni7 phase on XRD pattern are observed when x ≤ 0.92, and with decreasing x, the intensity of La2Ni7 diffraction peaks increases and the values of lattice parameters a and cell volume increase, c and c/a of LaNi5 phase decrease gradually. When x≥0.96, La2Ni7 phase disappears and the alloys become single CaCu5-type. The electrochemical tests show that the maximum discharge capacity, high rate dischargeability and low temperature dischargeability are improved to different degrees by adjusting the stoichiometric ratio.     

Effect of cobalt content on electrochemical performance of La-Mg-Ni system （Ce2Ni7-type） electrode alloys

In order to improve the cyclic stability of La-Mg-Ni system （Ce2Ni7-type） alloy electrode, small amount of Co was added in La0.75Mg0.25Ni3.5 alloy. The effect of Co on electrochemical performance and microstructure of the alloys were investigated in detail. XRD results showed that the alloys had multiphase structure composed of （La, Mg）2Ni7, LaNi5 and small amount of LaNi2 phases. The discharge capacity of the alloys first increased and then decreased with increasing Co content. At a discharge current density of 900 mA/g, the HRD of the alloy electrodes increased from 81.3% （x=0） to 89.2 % （x=0.2）, and then reduced to 87.8 % （x=0.6）. After 60 charge/discharge cycles, the capacity retention rate of the alloys enhanced from 52.67% to 61.32%, and the capacity decay rate of the alloys decreased from 2.60 to 2.05 mAh/g per cycle with increasing Co content. The obtained results by XPS and XRD showed that the fundamental reasons for the capacity decay of the La-Mg-Ni system （Ce2Ni7-type） alloy electrodes were corrosion and oxidation as well as passivation of Mg and Lain alkaline solution.     

Effect of praseodymium substitution for lanthanum on structure and properties of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1（X=0.00-0.20） hydrogen storage alloys

In order to investigate the effect of substituting La with Pr on structural and hydrogen storage properties of La-Mg-Ni system (AB3.5-type) hydrogen storage alloys, a series of La0.65-xPrxNd0.12Mg0.23Ni3.4Al0.1(x=0, 0.10, 0.15, 0.2) hydrogen storage alloys were prepared. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) analyses revealed that two alloys (x=0.0 and 0.10) were composed of (La, Mg)2(Ni,Al)7 phase, La(Ni,Al)5 phase and (La,Mg)Ni2 phase, while other alloys (x=0.15 and 0.20) consisted of (La,Mg)2(Ni,Al)7 phase, La(Ni,Al)5 phase, (La,Mg)Ni2 phase and (La, Mg)(Ni,Al)3 phase. All alloys showed, however, only one pressure plateau in P-C isotherms. The Pr/La ratio in alloy composition influenced hydrogen storage capacity and kinetics properties. Elec-trochemical studies showed that the discharge capacity decreased from 360 mAh/g (x=0.00) to 335 mAh/g (x=0.20) as x increased. But the high-rate dischargeability (HRD) of alloy electrodes increased from 26% (x=0.00) to 56% (x=0.20) at a discharge current density of Id=1800 mA/g. Anode polarization measurements were done to further understand the electrochemical kinetics properties after Pr substitution.     

Preparation and Structure of Mg2-xRExNi （RE = La, Ce, Pr, Nd, Y） Ternary Alloys

A series of Mg2-xNdxNi (x =0.05, 0.1, 0.2, 0.3) alloys and Mg1.95RE0.05Ni (RE= La, Ce, Pr, Nd, Y)ternary alloys were prepared by ball milling of mixted powder of Mg, Ni, RE and sintering under the protection of argon. XRD analysis shows that Mg2-xNdxNi (x = 0.05, 0.1 ) and Mg1.95RE0.05Ni consist of single phase with the same crystal structure as Mg2Ni. While three-phase alloys including Mg2Ni, NdNi and NdMgNi4 were formed in Mg1.8Nd0.2Ni and Mg1.7Nd0.3Ni alloys respectively. The lattice constants of Mg2Ni in those ternary alloys were calculated. The decomposition of Mg2Ni occurs in the milling process of Mg2Ni and Mg1.95RE0.05Ni alloys respectively. For the latter, another earlier reaction occurs in milling process, which means that atoms of RE are separated from crystal structure of Mg2Ni and form relevant oxides by combination with oxygen existed in argon atmosphere.     

Comparative Study on Thermodynamical and Electrochemical Behavior of Al（88）Ni6La6 and Al（86）Ni6La6Cu2 Amorphous Alloys

Two amorphous ribbons with the compositions of Al88Ni6La6 and Al86Ni6La6Cu2 were made using the melt-spun method,and their thermal response and electrochemical behavior were studied comparatively.Differential scanning calorimetry（DSC）and electrochemical polarization measurements indicated that Al86Ni6La6Cu2 exhibited slightly higher crystallization temperature（Tx）,lower melting point（Tl）and better corrosion resistance in 0.01 mol·L-1 NaCl alkaline solution.These results demonstrated that Cu（2%）addition could slightly promote the glass forming ability,but it could greatly improve the corrosion resistance of Al88Ni6La6 alloy in 0.01 mol·L-1 NaCl alkaline solution.     

Microstructures and electrochemical properties of LaNi3.8-xAlx hydrogen storage alloys

The microstructures and electrochemical properties of LaNi3.8-xAlx (x=0.0,0.1,0.2,0.3 and 0.4) alloys were studied systematically. The microstructures were identified by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The main phases were not changed with the substitution of Ni by Al, but minor phases appeared when x=0.4. With Al content increasing, the cell volume increased and the hydrogen storage capacity increased first and then decreased, and the maximum discharge capacity increased from 209.4 mAh/g (x=0.0) to 285.3 mAh/g (x=0.3) and then decreased to 241.3 mAh/g (x=0.4). Meanwhile, the exchange current density (I0) increased and the diffusion coefficient (D) decreased with the addition of Al.     

Mg_2Ni系储氢合金电化学性能的研究

用固态扩散和机械球磨法制备出纳米级Mg2 Ni和Mg1 .7Al0 .3 Ni储氢合金 ,其电化学性能超过用传统方法制备的合金。充放电测试表明 :该合金放电电压平台 (电压超过 1 2V)较高 ;在 2 0 0mA/g放电电流密度下 ,合金充放电循环 50次 ,容量仍保持在 2 0 0mAh/g以上。X射线衍射分析表明 :随着球磨时间延长 ,衍射峰的宽化程度变大 ,强度逐渐减弱 ,1 2h后变化减缓。这是由于晶粒尺寸变小 ,缺陷及应力密度增加之故。合金电化学性质的改善与合金在机械研磨中的微结构变化有关 ,并且合金组成中铝部分取代镁对于延长合金的循环寿命有至关重要的作用。     

Phase forming law and electrochemical properties of A2B7-type La-Y-Ni-based hydrogen storage alloys with different La/Y ratios

The effects of different proportions of La and Y elements in the A-side on the structure and properties of A₂B₇-type La-Y-Ni hydrogen storage alloys were investigated.The(La,Y)₂Ni₇ hydrogen storage alloys with different La/Y ratios were prepared by sintering the Y₂Ni₄ precursor and different AB₅-type precursors at 1298 K for 5 h and subsequently annealed for 20 h at 1248 K.All the alloys only contain Ce₂Ni     

An investigation on electrochemical hydrogen storage performances of Mg-Y-Ni alloys prepared by mechanical milling

The nanocrystalline and amorphous Mg2Ni-type electrode alloys with a composition of Mg20?xYxNi10 (x=0, 1, 2, 3 and 4) were fabricated by mechanical milling. Effects of Y content on the structures and e...     

LaMg11Zr+200%Ni+x%La(x=O,5,10)储氢合金结构及电化学性能

采用机械合金化法(MA)制备了非晶态LaMg11Zr+200%(质量分数,下同)Ni+x%La(x=0,5,10)系列储氢合金,并详细研究了La添加对该系列合金的相结构及电化学性能的影响.结构分析表明,球磨20h该系列合金都呈非晶态,La添加后合金颗粒得到明显细化;电化学研究表明,La添加后,合金电极充电阻力减小,放电容量随La含量的增加而增大,适量v的添加一定程度上改善了合金电极的循环稳定性和动力学性能,LaMg11Zr+200%Ni+5%La合金电极达到最大放电容量597.2mAh·g-1,循环30次后的容量保持率仍为53.5%.     

Influence of rapid quenching on cyclic stability of La-Mg-Ni system （AB3-type） electrode alloys

Aiming at the improvement of the cyclic stability of La-Mg-Ni system （PuNi3-type） hydrogen storage alloy, Ni in the alloy was partly substituted by Fe. The electrode alloys of La0.7Mg0.3Co0.45Ni255-xFex （x=0, 0.1, 0.2, 0.3, 0.4） were prepared by casting and rapid quenching. The influence of the quenching on cyclic stability as well as structure of the alloys was investigated in detail. The results of electrochemical measurement indicated that rapid quenching significantly improved cyclic stability. When the quenching rate rose from 0 （As-cast was defined as a quenching rate of 0 m/s） to 30 m/s, the cyclic life of Fe-free alloy （x=-0） increased from 81 to 105 cycles, and for alloy containing Fe（x=0.4）, it grew from 106 to 166 cycles at a current density of 600 mA/g. The results obtained by XRD, TEM and SEM revealed that the as-cast and quenched alloys had multiphase structures, including two major phases （La, Mg）Ni3 and LaNi5 as well as an imptLrity phase LaNi2. Rapid quenching helped the formation of an amorphous-like structure in Fe containing alloys.     

Effect of Spark Plasma Sintering Temperature on Electrochemical Properties of La0.82Mg0.18Ni3.50Co0.15 Alloy

Electrochemical properties of La_(0. 82)Mg_(0. 18)Ni_(3. 50)Co_(0. 15) alloys synthesized by spark plasma sintering( SPS) were investigated based on the electrochemical measurements,physical parameters and microstructure observation. The sintering behavior of La_(0. 82)Mg_(0. 18)Ni_(3. 50)Co_(0. 15) alloys at the temperatures of 900,950 and 1 000 ℃ is characterized by four stages,i. e.,initial slight shrinkage,expansion,abrupt shrinkage and slight expansion. The maximum shrinkage displacement increases with increasing sintering temperature. All of the alloys consist of( La,Mg)_2( Ni,Co)_7 phase; additionally,temperatures of 900 and 950 ℃ are beneficial to the formation of( La,Mg)( Ni,Co)_3 phase,whereas the LaNi_5 phase is easy to form in the alloy synthesized by SPS at 1 000 ℃. The electrochemical measurements indicate an evident change of the electrochemical performance of the alloys associated with increasing the sintering temperature. The discharge capacity of the alloys first increases and then decreases as sintering temperature rises,whereas their cycle stability clearly grows all the time.Furthermore,the charging-discharging potential difference and discharging efficiency both demonstrate that the electrochemical properties of the alloy electrodes first augment and then decline with increasing sintering temperature.     

La0.75Mg0.25Ni3.47Co0.2Al0.03储氢合金电极失效研究

采用中频感应真空熔炼制备La0.75Mg0.25Ni3.47Co0.2Al0.03合金,并借助电化学和气态循环实验、SEM、XPS等手段对合金电极失效的原因进行研究.结果表明,合金放电容量和吸氢容量的衰减在循环过程中均分为快速和缓慢两个阶段.随循环次数的增加,在电化学循环过程中,合金颗粒表面的氧化腐蚀产物逐渐增多,接触电阻和电荷传递电阻先降低后提高;在气态吸放氢过程中,合金颗粒裂纹逐渐增多,且开裂程度增大.La和Mg的氧化腐蚀损耗是导致合金放电容量衰减的主要原因,而合金颗粒粉化加剧了La、Mg的腐蚀,进一步恶化合金电极的稳定性.