镍氢电池用贮氢合金多元化降钴的研究

 为了降低贮氢合金中的钴含量，从而降低镍氢电池的价格，在贮氢合金MlNi355Co075Mn04Al03的基础上，依次添加铜、铬、锌及铁元素，得到稀土基多元贮氢合金，并测试和分析了它们的放电容量、循环稳定性以及微观结构。结果表明，采用适量的铜、铬、锌及铁替代钴所得到的低钴贮氢合金仍具有较高的放电容量和较好的循环稳定性，而且其相结构并未改变。     

Electrochemical Properties of Sn Doped AB_5 Non-Stoichiometric Hydrogen Absorbing Alloys-Ⅱ

Ｒａｒｅｅａｒｔｈｈｙｄｒｏｇｅｎａｂｓｏｒｂｉｎｇａｌｌｏｙｓａｒｅｗｉｄｅｌｙｕｓｅｄｉｎｎｉｃｋｅｌ ｍｅｔａｌｌｉｃｈｙｄｒｉｄｅｂａｔｔｅｒｉｅｓ(Ｎｉ ＭＨ )ｂｅｃａｕｓｅｏｆｔｈｅｈｉｇｈｐｅｒｆｏｒｍａｎｃｅｃｈａｒａｃｔｅｒｉｓｔｉｃｓｏｆｔｈｅｓｅｍａｔｅｒｉａｌｓｉｎｒｅｓｐｅｃｔｔｏｅｎｅｒｇｙｄｅｎｓｉｔｙ ,ａｃｔｉｖａｔｉｏｎａｎｄｃｙｃｌｉｎｇｌｉｆｅ .ＴｈｅｒａｔｅｃａｐａｂｉｌｉｔｙｏｆＮｉ ＭＨｂａｔｔｅｒｉｅｓｍｕｓｔｂｅｉｍｐｒｏｖｅｄｇｒｅａｔｌｙｂｅｃａｕ…     

镍氢电池负极用低成本储氢合金的研究

研究了ABS型储氢合金在低Co含量条件下，随B组元替代元素Co，Al，Si等含量的变化对合金电化学性能的影响规律，同时研究了A组元中不同La／Ce比对合金电化学性能的影响情况。结果表明，随合金中Co含量的降低，合金的活化性能和放电容量得以改善，但合金的循环寿命下降也比较明显；在试验范围内，随Al元素的加入，合金的循环寿命得以改善，但材料的放电容量和活化性能均有所下降；随合金La／Ce比的降低，合金的放电容量略有下降，但其循环寿命和放电电压平台有较大提高。     

低钴稀土系贮氢合金的研究

通过在稀土系贮氢合金中添加不同含量的Fe或Cu元素,部分替代合金中Co的方法,研究低钴贮氢合金电化学性能上的差异.结果表明:由于合金组成和化学计量比的不同,同样是添加了Fe或Cu的合金在电化学性能上表现不同,但总体说,含Cu低钴贮氢合金容量和倍率放电性能较好,含Fe低钴贮氢合金有较好的循环稳定性,过化学计量比的合金循环稳定性要好于欠化学计量比的合金.     

Phase Structure and Electrochemical Properties of RE-Mg Based Composite Hydrogen Storage Alloys

Rareearth basedAB5 typealloy ,akindofhy drogenstoragealloyusedasnegativeelectrodemateri alsofthenickel/metalhydride (Ni/MH )secondarybattery ,haseasyinitialactivation ,longcyclelifeandlowcost ,butstillasmalldischargecapacity ,poorhigh ratedischargeability(HRD)andpoorpropertiesatlowtemperature[1,2 ] .Therefore ,howtoincreaseitsdischargecapacityandtoimproveotherelectrochemi calpropertiesismeaningfulbothintheoryandinpracticalapplication .Mg basedhydrogenstorageal loysareremarkablebecauseofitsr…     

AB5型含Mn储氢合金的研究综述

文章评述了近年来人们对提高AB5型含Mn储氢合金综合性能所进行的研究。通过综述AB5型含Mn稀土系储氢合金Mn在合金中的作用及Mn含量变化、显微结构等对储氢合金的影响,得出储氢合金中Mn对吸氢平台压力、储氢容量、吸放氢速率、循环寿命的影响。通过利用Mn元素对B侧元素的部分或全部替代或Mn被其它元素替代,可以对AB5型储氢合金进行更深入研究,从而进一步提高其综合性能。     

AB5型与AB3.5型贮氢合金的电化学性能对比研究

为了对比研究AB5型与AB3.5型贮氢合金的电化学及动力学特性,以AB5型MlNi3.68Mn0.32Co0.73Al0.27和AB3.5型Ml0.80Mg0.20 （NiMnAlCu）3.6、La0.6 Mg0.4 Ni3.5为研究对象.采用XRD分析了合金的相结构,利用电化学方法测试合金的电化学及动力学特性.结果发现,MlNi3.68 Mn0.32Co0.73Al0.27合金由单相LaNi5相组成,而Ml0.80Mg0.20（NiMnAlCu）3.6、La0.6Mg0.4Ni3.5均有LaNi5相和La2Ni7相组成.AB3.5型合金的放电容量、荷电保持率以及动力学特性高于AB5型合金.     

用HAc-NaAc缓冲溶液对AB_5型储氢合金表面改性的研究

用ＨＡｃ－ＮａＡｃ缓冲溶液对ＡＢ５型储氢合金进行表面改性，通过ＸＲＤ、化学分析和恒电流充放电方法进行比较研究发现：这一方法没有改变合金的主体结构，但改变了合金表面层中的元素组成，这对于储氢合金的初期容量的提高有一定作用。     

多元化降钴对贮氢合金性能的影响

为了降低贮氢合金中的钴含量，从而降低镍氢电池的价格，在贮氢合金M1Ni3．55Co0．75Al0．3Mn0．4的基础上，依次添加Cu、Cr、Zn、Fe元素，得到稀土基多元贮氢合金，并对其放电容量和循环稳定性进行了测试和分析。结果表明，适量的Cu、Cr、Zn、Fe替代Co，仍能使贮氢合金具有较高的放电容量和较好的循环稳定性。     

钒基固溶体型贮氢合金的研究进展

金属钒具有吸氢量大、抗粉化性能好等优点，但是有效吸氢量较低，只有一半的氢能够释放出来，没有实用价值。在V-Ti二元合金的基础上形成的三元合金V-Ti-M(M代表Cr，Mn，Fe，Ni等)具有良好的贮氢性能。Ti／Cr比对V-Ti-Cr合金性能影响很大，Ti/Cr比值为0．75时V-Ti-Cr合金具有最大的贮氢量和有效吸氢量，同时热处理可以有效地提高V-Ti-Cr合金的有效吸氢量，并降低V的使用量。添加Mn的三元合金具有BCC和Laves相双相结构。V-Ti-Fe合金的贮氢量很高，并有希望利用便宜的钒铁做钒源。此外，V基固溶体合金还可以用于镍氢电池负极，如V-Ti-Ni合金具有很高的放电容量，目前需要解决其循环稳定性差和成本高的问题。     

热处理对La_(0.53)Ce_(0.47)Ni_(3.4)Co_(0.6)Mn_(0.3)Cu_(0.1)合金相结构和储氢性能的影响

采用感应熔炼法制备La_(0.53)Ce_(0.47)Ni_(3.4)Co_(0.6)Mn_(0.3)Cu_(0.1)储氢合金,并在不同温度下进行热处理,通过XRD对其相组成及结构进行表征,并采用双电极模拟电池测试系统对其储氢性能进行测试与分析。结果表明,随着退火温度的升高,合金的相组成未发生变化,但其晶化程度逐渐增高,晶体缺陷和晶格应力逐渐减少。热处理改善了合金的循环稳定性,提高了合金的电化学容量,但恶化了高倍率放电能力。     

Application of Nanocrystalline LaNi5-type Hydrogen Absorbing Alloys in Ni-MHx Batteries

Duringlastyears ,interestinthestudyofnanos tructuredmaterialshasbeenincreasing .Thisisduetorecentadvancesinmaterials′synthesesandcharacteri zationtechniquesandtherealizationthatthesemateri alsexhibitmanyinterestingandunexpectedphysicalaswellaschemicalpropertieswithanumberofpoten tialtechnologicalapplications .Forexample ,hydrogenstoragenanomaterialsarethekeytothefutureofthestorageandbatteries/cellsindustries[1,2 ] .TheTiFe ,ZrV2 andLaNi5phasesarefamiliarmaterialswhichabsorblargequantitiesof…     

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 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.     

气雾化低钴贮氢AB_5型合金的电化学性能和Rietveld分析

用快速凝固气体雾化法制备了低钴系列贮氢合金MlNi4 .3 -xCoxMn0 .4 Al0 .3 (x =0 75 ,0 45 ,0 2 9,0 1,Ml为富镧混合稀土 )并测试其电化学性能。气雾化法可显著提高贮氢合金电极的充 放电循环稳定性 ,x =0 45时合金的循环寿命与商用铸态合金的寿命相当。最大放电容量随着Co含量的增加 ,先增大后减小 ,在x=0 2 9时出现极大值 (30 4 4mAh/g)。结合循环寿命和最大放电容量两个性能指标 ,x =0 45时的合金具有良好的综合电化学性能。采用Rietveld法 (多晶衍射图形拟合法 )对其精细结构进行分析 ,合金仍保持母合金LaNi5的CaCu5型六方晶系结构 ,合金的晶胞体积对其循环寿命和最大放电容量起决定作用     

热处理对贮氢合金电化学性能的影响

研究了热处理工艺氢合金活化性能,初始放电容量,稳定放电容量,电压平台及循环寿命等电化学性能的影响,并确定了合适的热处理工艺。     

宽温型AB5储氢合金结构及其电化学性能研究

用高频感应熔炼法制备了Mm(NiCoAlMn)5储氢合金,采用模拟电池法测试了合金在238～323 K温度范围内的活化、放电容量和高倍率放电性能.结果表明:制备合金为典型AB5型储氢合金,303K温度条件下吸氢量达到1.38％(质量分数),氢化物生成焓为32.36 kJ ·mol-1H2.合金电极的活化性能、放电容量和高倍率性能受温度影响显著.室温预活化可有效改善电极的低温性能,经室温预活化后合金电极在238 K最大放电容量达到336 mAh·g -1,明显高于未经室温预活化的最大放电容量25 mAh·g-1.Mm(NiCoMn)5贮氢合金电极的高倍率性能随着温度的升高先升高后降低,273和303 K温度条件下合金保持高倍率性能良好,3C放电电流密度条件下容量保持率均高于80％;238 K温度条件下合金的大电流放电性能急剧降低,1C放电电流密度条件下容量保持率仅为10％; 273 K下合金电极的综合性能最佳,最大放电容量达到340 mAh·g-1,300 mA·g-1放电电流密度下的高倍率放电比率为86％.循环伏安法测试证实,在238～323 K范围内,电极的氧化峰峰值电流(Ip)与扫描速度的平方根(v1/2)之间均存在良好的线性关系,整个电极反应受氢原子扩散控制;随着温度的降低氢扩散系数急剧下降,从而导致该合金电极的低温高倍率放电性能变差.由Arrhenius公式计算出合金中的氢扩散活化能为10.56 kJ·mol -1.     

Composition optimization and electrochemical characteristics of Co-free Fe-containing AB5-type hydrogen storage alloys through uniform design

In order to reduce the cost of AB5-type hydrogen storage alloys, effects of substitution of Ce for La (A side) and Fe, Mn, Al for Ni (B side) on structural and electrochemical properties of (LaCe)1(NiFeMnAl)5 alloys were studied systematically. To make component uniform and operation easy, uniform design (UD) method was introduced into the study of composition optimization of Co-free Fe-containing AB5-type alloys for the first time. X-ray diffraction (XRD) results showed that the designed alloys were of single CaCu5-type structure phase. The replacement of Fe had a severe effect on electrochemical capacity, and the substitution of Fe and Al had a synergetic action among the unit cell volume, cycling stability and high rate discharge property. Interestingly, it was found that the hydrogen storage alloys with exces-sively high plateau pressure showed a tilted line in Nyquist plot instead of the semicircle, and the current decayed rapidly to near zero at the beginning of the step in constant potential step (CPS), indicating that electrochemical impedance spectra (EIS) and CPS cannot accurately measure the electrochemical kinetics process of the hydrogen storage alloys with excessively high plateau pressure.     

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.     

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.