镁基非晶电极合金的容量衰减机制探讨

采用熔体快淬法制备了(Mg70.6Ni29.4)100-xNdx(x=2,5,10,15)电极合金带,用恒流充放电的方法在三电极电池测试仪上测定其电化学循环性能。用X射线衍射仪、场发射扫描电镜和高分辨电镜对合金在充放电循环过程中的组织结构变化进行了动态检测。结果表明:(Mg70.6Ni29.4)90Nd10非晶电极合金拥有最高的放电容量(580.5 mAh·g-1),经过20个循环以后,合金表面存在严重的氧化(含氧量为26.7%)和开裂粉化现象;在充放电循环过程中,合金内部逐渐形核长大,形核的初生相NdMg2Ni9最终转化为Mg2Ni,α-Mg和Nd2H5相;非晶态Mg-Ni-Nd电极合金在充放电循环过程中放电容量的衰减来自于内外两个方面的综合效应:合金表面碱液的氧化腐蚀和开裂粉化以及非晶合金的晶化导致其贮氢机制失效,反应动力学性能下降,从而引起放电容量的衰减。     

Mg2Ni系储氢合金电化学性能的研究

用固态扩散和机械球磨砺法制备出纳米级Ｍｇ２Ｎｉ、Ｍｇ１．７Ａｌ０．３Ｎｉ储合金，其电化学性能超过用传统方法制德的合金。驻卵是试表明：该合金放压平台（电压超过１．２Ｖ）较高：在２００ｍＡ／ｇ放电电流密度下，合金充放电循环５０次，容量仍保持在２００ｍＡｇ／ｇ以上。Ｘ射线行射分析表明；随着球磨时间延长，衍射峰的宽化程度变大，强度逐渐减弱，１２小时后变化减缓。这是由于晶粒尺寸较小。缺陷及应力密度增加入。合     

钒钛系新能源电池负极合金的球磨参数优化研究

采用不同机械球磨工艺参数进行了钒钛系电池负极合金V-20.5Ti-14Ni-6Co-4Al制备,并进行了充放电循环稳定性和耐腐蚀性能的测试与对比分析。结果表明:球磨转速和球磨时间对合金充放电循环稳定性和耐腐蚀性能产生明显影响。随球磨转速从300 r/min增至700 r/min、球磨时间从2 h延长至10 h,合金的充放电循环稳定性和耐腐蚀性能均先提高后下降。合金的球磨转速优选600 r/min、球磨时间优选6 h。与球磨转速300 r/min相比,球磨转速600 r/min时合金的放电容量衰减率减小16个百分点、腐蚀电位正移了81 mV。与球磨时间2 h相比,球磨时间6 h时合金的放电容量衰减率减小18个百分点、腐蚀电位正移了116 mV。     

镧取代对镁基贮氢合金的影响及其电化学性能研究

用机械球磨法(MA)合成了Mg0.9LaxAl0.1-xNi(x=0.015,0.02,0.025,0.03)系列合金。充放电性能测试表明金属Mg被La取代后,合金放电容量的衰减变缓,最高放电容量为418.64 mAh.g-1,30周以后仍能达到161.41 mAh.g-1。XRD结构分析表明,在球磨初期仍为晶态,随着球磨时间的增加,逐渐变为非晶态,此时放电容量达到最大。循环伏安和交流阻抗测试结果表明当La的取代含量为0.025时电化学容量最高,循环可逆性好且电极表面电子转移电阻即电化学反应电阻最小。     

添加钕对Mg2Ni储氢合金的结构和电极性能的影响

利用两步法制备了一系列添加Nd的三元Mg2-xNdxNi合金。XRD分析证实，当x=0．05，0．1时，制得的三元Mg2-xNdxNi合金均为Mg2Ni单相合金；三元Mg18Nd0．2Ni(x=0．2，0．3)合金为三相合金，三相分别为Mg2Ni，NdNi，NdMgNi4。模拟电池测试结果表明，同Mg2Ni合金相比，球磨10h的三元Mg1．8Nd0．2Ni合金和Mg17Nd03Ni合金电极的放电容量提高明显，且Mg17Nd03Ni合金电极的循环性能有明显改善。这极有可能与合金中NdMgNi4相的存在以及球磨形成的微结构有关。     

Co替代Ni对A2B7型贮氢电极合金相结构及电化学性能的影响

采用感应熔炼方法制备了La0.75Mg0.25Ni3.5-xCox(x=0,0.25,0.75,1)四元贮氢合金,系统地研究了合金B侧Co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-xCox由(La,Mg)2Ni-7相(包括Gd2 Co7型高温相和Ce2 Ni7型低温相)组成.此外,随着Co元素的加入,该类合金中出现CaCu5型LaNi5相.电化学测试表明,随Co含量的增加,合金电极活化次数增大,合金电极的最大放电容量增大,合金的最大放电容量由x =0.25时的376.53 mAh/g增加到x=1时的401.62mAh/g,氢扩散系数增大,循环稳定性变差,合金的高倍率放电性能降低,Co含量对合金电极高倍率放电性能HRD值的影响与对合金电极交换电流密度的影响趋势一致,这表明电极合金表面的电化学反应对合金的动力学性能影响更大.     

纳米晶富铈稀土储氢合金制备及电化学性能

通过双辊快淬法制备的AB5型富铈稀土储氢合金,经X射线衍射(XRD)、扫描电镜(SEM)以及元素分析(ICP),表明该合金具有纳米晶结构,其组成成分为La0.37Ce0.41Pr0.1Nd0.12Ni4.0Co0.45Mn0.3Al0.25.同时对合金电化学性能以及循环性能进行了表征,在100mA/g放电比容量为295mA·h/g,用300 mA/g充放电120次循环后,容量衰减仅为4.8%.     

A2B7型La0.75Mg0.25Ni3.5-xFex(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-xFex(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侧Fe对Ni部分替代对合金相结构及电化学性能的影响.X射线衍射(XRD)分析表明,La0.75Mg0.25Ni3.5-xFex由(La,Mg)2Ni7相(包括Gd2Co7型高温相和Ce2Ni7型低温相)组成.此外,随着Fe元素的加入,该类合金中出现CaCu5型LaNi5相,且随着Fe含量的增加而增多.电化学测试表明,随Fe含量的增加,合金电极活化次数变化不大,而其最大放电容量呈现先增后减的趋势,合金的最大放电容量由x=0.05时的376.21 mAh·g -1下降到x=0.3时的340.89 mAh·g-1;合金的高倍率放电性能随着Fe含量的增加而降低,当电流密度为900 mA·g-1时,合金的高倍率放电性能由83.66%(x=0)减小到62.23%(x=0.3);循环稳定性先增加后下降.     

热处理对La0.65Pr0.05Nd0.05Mg0.25Ni3.3Al0.1储氢合金结构和电极性能的影响

为了了解新型稀土-镁-镍系储氢合金的结构和电化学性能与热处理温度的关系,通过中频感应熔炼法制备了La0.65Pr0.05Nd0.05Mg0.25Ni3.3Al0.1储氢合金,在氩气保护下进行退火热处理,温度为1123K、1173K和1223K,保温时间8h.应用X射线衍射、扫描电镜、能谱分析等方法研究了合金的结构,测试了合金的主要电化学性能.结果表明该合金由三相组成(La,Mg)Ni3.5相、LaNi5相和(La,Mg)Ni2相,退火后三相的相对含量发生了变化, 随着热处理温度的逐步提高,合金中LaNi5相和(La,Mg)Ni2相的比例减小,(La,Mg)Ni3.5相的比例增加.合金的放电容量、充放电循环稳定性与合金组成相所占比例密切相关, 尤其是(La,Mg)Ni2相的存在不容忽视.     

元素替代及导电剂对Y_2FeSb_2合金结构和电化学性能的影响

利用电弧熔炼法制备了元素取代前后的Y2FeSb2合金。XRD结果表明,未取代的合金由单一的YSb相组成,La部分取代Y使合金的晶格常数增加,而Ni部分替代Sb的合金由主相YSb相和少量的YNi2、YNi相组成,同时主相的晶格常数也略有增加。电化学测试表明,以Ni粉为导电剂时,La部分取代Y使合金的放电容量有所下降,从34.8 mAh/g下降到了27.3 mAh/g,而Ni替代Sb使合金的放电容量从34.8 mAh/g增加到了51.3 mAh/g,同时使放电电压提高了20 mV,La和Ni同时替代使二者增加的幅度更加明显,特别是放电电压在第50次循环后提高了约300 mV。当Cu粉为导电剂时,Y2FeSb2合金表现出了较大的放电容量(792.6 mAh/g),而La和Ni同时替代后的Y1.5La0.5FeSbNi合金放电容量更是达到了880.8 mAh/g,这主要是由于合金粉和Cu粉在充放电过程中相互作用的缘故。     

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.     

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).     

Structure and electrochemical hydrogen storage characteristics of Ce-Mg-Ni-based alloys synthesized by mechanical milling

The substituting Mg with Ni and milling as-cast alloy with Ni were adopted to obtain nanocrystalline/amorphous CeMgnNi+x wt.%Ni(x=100,200) alloys and promote the electrochemical hydrogen storage performances of CeMg_(12)-type alloys.Analyzing the structural features of the alloys provided a mechanism for ameliorating the electrochemical hydrogen storage properties.The electrochemical tests demonstrated that all the alloys just needed one cycle to be activated.Rising Ni proportion had an obvious role on charge-discharge reaction.The discharge capacities of the as-milled(60 h) alloys increased sharply from 182.0 mAh/gfor x=100 alloy to 1010.2 mAh/gfor x=200 alloy at current density of 60 mAh/g.Furthermore,milling time largely determined the performances of electrochemical reaction.The discharge capacity continued to grow along with prolonging milling time,while the cycle stability obviously decreased for x=100 alloy,and first declined and then augmented for the x=200 alloy with milling time extending.In addition,there was an optimal value with milling time varying for the high rate discharge abilities(HRD),which was 80.3%for x=100 alloys and 86.73%for x=200,respectively.     

Structure and electrochemical hydrogen storage characteristics of the as-cast and annealed La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 （x=0-0.4） alloys

In order to ameliorate the electrochemical cycle stability of the RE-Mg-Ni based A2B7-type electrode alloys, the Mg content in the alloy was reduced and La in the alloy was partially substituted by Sm. The La0.8-xSmxMg0.2Ni3.15Co0.2Al0.1Si0.05 (x=0, 0.1, 0.2, 0.3, 0.4) elec-trode alloys were fabricated by casting and annealing. The microstructures of the as-cast and annealed alloys were characterized by XRD and SEM. The electrochemical hydrogen storage characteristics of the as-cast and annealed alloys were measured. The results revealed that all of the experimental alloys mainly consisted of two phases: (La,Mg)2Ni7 phase with the hexagonal Ce2Ni7-type structure and LaNi5 phase with the hexagonal CaCu5-type structure. As Sm content grew from 0 to 0.4, the discharge capacity and the high rate discharge ability (HRD) first in-creased and then decreased for the as-cast and annealed alloys, whereas the capacity retaining rate (S100) after 100 cycles increased continuously.     

Effects of annealing on microstructures and electrochemical properties of La0.8Mg0.2Ni2.4Mn0.10Co0.55Al0.10 alloy

The La0.8Mg0.2Ni2.4Mn0.10Co0.55Al0.10 alloy was prepared by induction melting. The structural and morphological characterizations were performed by means of X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical measurements were performed using LAND and CHI 660b electrochemical workstation. The main phases of the alloy were LaNi5 and (La,Mg)Ni3. After annealing, the maximum discharge capacity, cycle stability and high rate dischargeability (HRD) were improved obviously. The maximum discharge capacity reached 373.80 mAh/g (T=1173 K), the C100/Cmax(%) was 72.63% (T=1173 K), and the value of HRD reached 51.8% at a discharge current density of 1150 mA/g (T=1173 K). The cyclic voltammetry (CV) and potentiodynamic polarization were also studied.     

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.     

硼的添加对Mg2Ni储氢合金吸放氢性能的影响

镁系储氢合金有着价格低廉、储氢量大等优点,作为机载储氢材料有着广泛的应用前景,但其过高的氢分解温度,过慢的分解速度等缺点制约着实际应用.采用机械球磨制备出Mg2 Ni-xB(x =0％,1％,5％,10％,15％)系列储氢合金.通过XRD分析了合金的物相结构,采用P-C-T测试仪测定了合金的吸放氢性能,研究了添加不同含量的B对Mg2Ni合金吸放氢性能的影响.研究结果表明,B的添加对合金在200和300℃下吸放氢性能的改善作用不明显,但添加B的合金在400℃下的吸氢量均较Mg2Ni高,B的添加量由1％增至15％的合金吸氢量分别为3.09％,3.00％,2.81％,2.84％,而Mg2Ni的吸氢量则只有2.60％.随着B含量的增加,含B合金吸氢量略有降低;在含B的试样中,含5％B的合金吸氢速率最大,仅需180 s便能完成吸氢.所有含B合金的放氢平台均较Mg2Ni高且较为平坦.本次实验表明,B的添加量对合金性能的提升存在一个最优值,本次实验结果显示,添加5％B相对较好地改善合金的储氢性能,提高合金吸氢量和放氢平台压的同时能保持较快的吸氢速率.     

Study on structure and electrochemical properties of the （LaGdMg）Ni3.35-xCoxAl0.15（x=0-2.0） hydrogen storage alloys

Hydrogen storage alloys(LaGdMg)Ni3.35-xCoxAl0.15(x=0,0.1,0.3,0.5,1.0,1.5,2.0) were prepared by induction melting followed by annealing treatment in argon atmosphere.The effects of partly replacing Ni by Co element in(LaGdMg)Ni3.35Al0.15 on the phase structure and electrochemical properties of(LaGdMg)Ni3.35-xCoxAl0.15 alloys were investigated.Structure analysis showed that the alloys consisted of Ce2Ni7-type(Gd2Co7-type),CaCu5-type,Pr5Co19-type,PuNi3-type phase structure.The addition of Co element obviously reduced the contents of CaCu5-type phase and increased the contents of Ce2Ni7-type phase.However,Pr5Co19-type and CaCu5-type phase obviously increased with the high content of Co.Rietveld analysis showed that the c-axis lattice parameters and cell volumes of the component phases increased with increasing Co content.The electrochemical measurements showed that as the Co content increased,the maximum discharge capacity and the cyclic stability of the annealed alloys both first increased then decreased.The(LaGdMg)Ni3.05Co0.3Al0.15 alloy electrode exhibited the maximum discharge capacity(392.92 mAh/g),and the(LaGdMg)Ni1.85Co1.0Al0.15 alloy electrode showed the best cyclic stability(S100=96.1%).     

A study on hydrogen storage and electrochemical properties of La_（0.55）Pr_（0.05）Nd_（0.15）Mg_（0.25）Ni_（3.5） （Co_（0.5）Al_（0.5））_x （x=0.0, 0.1, 0.3, 0.5） alloys

The La0.55Pr0.05Nd0.15Mg0.25Ni3.5(Co0.5Al0.5)x(x=0.0, 0.1, 0.3, 0.5) alloys were prepared by magnetic levitation melting under an Ar atmosphere, and the effects of Co and Al on the hydrogen storage and electrochemical properties were systematically investigated by pressure composition isotherms, cyclic voltammetry, Tafel polarization and electrochemical impedance spectroscopy testing. The results showed that the alloy phases were mainly consisted of (La,Pr)(Ni,Co)5, LaMg2Ni9, (La,Nd)2Ni7 and LaNi3 phases, and the cell volumes of (La,Pr)(Ni,Co)5, LaMg2Ni9, (La,Nd)2Ni7 and LaNi3 phases expanded with Co and Al element added. The hydrogen storage capacity initially increased from 1.36 (x=0) to 1.47 wt.% (x=0.3) and then decreased to 1.22 wt.% (x=0.5). The discharge capacity retention and cycle stability of the alloy electrodes were improved with the increase of Co and Al contents. The La0.55Pr0.05Nd0.15Mg0.25Ni3.5(Co0.5Al0.5)0.3 alloy electrode possessed better electrochemical kinetic characteristic.     

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.