硼对稀土系AB5型贮氢合金微观结构及电化学性能的影响

测试分析了稀土系AB5型贮氢合金MmNi3.8Co0.4Mn0.6Al0.2Bx(x=0, 0.1, 0.2, 0.3, 0.4)的微观结构及电化学性能, 研究了硼含量x对贮氢合金电化学性能及微观结构的影响.结果表明, 铸态贮氢合金具有双相组织, 主相为CaCu5型相, 还有少量CeCo4B第二相, 第二相的相丰度随x的增加而增大.对合金进行了不同淬速的快淬处理, 合金中第二相的量随淬速的增加而减少.硼的加入使合金的电化学容量下降, 但活化性能及循环寿命明显提高.特别是对于快淬态合金, 硼对因促进非晶的形成而显著提高循环寿命.     

Li掺杂对AB5型稀土贮氢合金相结构和电化学性能的影响

采用粉末烧结法,制备了一系列掺杂Li的AB5型稀土贮氢合金,并研究了Li掺杂量对贮氢合金MlNi3.55Mn0.40Al0.30Co0.70Lix相结构和电化学性能影响.结果表明:随Li掺杂量的增加,合金的晶胞参数c、c/a和晶胞体积V也随之增大;适量Li(x≤0.20)掺杂对合金的电化学容量有所提高,MlNi3.55 Mn0.40 Al0.30 Co0.70 Li0.20合金的0.2C放电容量达到273.53 mA·h/g;掺杂Li能改善合金的高倍率放电性能,当Li的含量为0.20～0.30时,合金的高倍率放电性能最好;掺杂Li能不同程度地提高贮氢合金的充放电循环稳定性,当x=0.20时,其循环性能最好,MlNi3.55Mn0.40Al0.30Co0.70Li0.20合金200次循环的电容与最大电容的比率(S200)达86.2%,但当Li掺杂量大于0.50时,合金的循环性能反而下降.     

Electrochemical properties of TiV-based hydrogen storage alloys

The electrochemical properties of the super-stoichiometric TiV-based hydrogen storage electrode alloys(Ti0.8Zr0.2)(V0.533Mn0.107Cr0.16Ni0.2)x(x=2,3,4,5,6)were studied.It is found by XRD analysis that all the alloys mainly consist of a C14 Laves phase with hexagonal structure and a V-based solid solution phase with BCC structure.The lattice parameters and the unit cell volumes of the two phases decrease with increasing x.The cycle life.the linear polarization.the anode polarization and the electrochemical impedance spectra of the alloy electrodes were investigated systematically.The overall electrochemical properties of the alloy electrode are found improved greatly as the result of super-stoicfhiometry and get to the best when x=5.     

Effect of commercial AB5 alloy addition on the electrochemical properties of Ml-Mg-Ni-based hydrogen storage alloys

A commercial AB5 hydrogen storage alloy was used as an additive to improve the electrochemical properties of Ml-Mg-Ni-based hydrogen storage alloys.The effect of AB5 alloy addition on the phase structure,charge/discharge characteristics,and electrochemical kinetics of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 alloy was investigated.The maximum discharge capacity of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 + 4 wt.% AB5 electrode reaches 406 mAh/g.The anodic polarization,cyclic voltammetry,and potential step discharge experiments show that the electrochemical kinetics of the electrode with additives was promoted,with the LaNi5 phase of AB5 alloy acting as electro-catalytic sites in the electrode alloy.The high-rate dischargeability of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 + 4 wt.% AB5 alloy electrode at 1100 mA/g reaches 60.9%,which is 9.4% higher than that of Ml0.90Mg0.10Ni3.08Mn0.13Co0.63Al0.14 alloy electrode.The cycling stability of the electrode with 4 wt.% AB5 alloy has also been improved.     

新型钛钒系贮氢电极合金

研究了新型钛钒系贮氢电极合金Ti0.8Zr0.2V2.665Mn0.535Cr0.8Ni的相结构、微观组织及电化学性能。XRD及EDS分析表明：铸态合金主要由C14 Laves相母体和树枝晶的钒基固溶体相组成，同时由于成分偏析的缘故，合金中还存在少量的TiNi基的第三相。热处理使得合金中C14 Laves相及钒基固溶体相的晶胞参数和晶胞体积增大，促进合金成分的均匀化，同时极大地改善了合金电极的综合电化学性能。     

非化学计量比贮氢合金Ml(Ni0.71Co0.15Al0.06Mn0.08)x的电化学性能

研究了化学配比x对贮氢合金Ml(Ni0 .71 Co0 .1 5Al0 .0 6Mn0 .0 8) x(4.6≤x≤ 5.2 )的结构、组织、电化学性能和 p c T特性的影响。结果表明 ,随着x增大非化学计量比合金点阵常数a值减小 ,c值增大 ,单胞体积减小 ,当x =5.2时c/a达到最大值。x =5.0的化学计量比合金具有最小的点阵常数和单胞体积。放电容量、充放电循环稳定性和 p c T曲线平台压均随着x增大而提高 ,当x =5.2时达到最大放电容量和最佳循环稳定性。     

Low-Co rare-earth-based hydrogen storage alloy

1　ＩＮＴＲＯＤＵＣＴＩＯＮＴｈｅｒａｒｅ ｅａｒｔｈ ｂａｓｅｄＡＢ5 ｔｙｐｅａｌｌｏｙｓｈａｖｅｂｅｅｎｉｎｖｅｓｔｉｇａｔｅｄｅｘｔｅｎｓｉｖｅｌｙａｓｅｌｅｃｔｒｏｄｅｍａｔｅｒｉａｌｓ.ＴｈｅｔｙｐｉｃａｌｃｏｍｐｏｓｉｔｉｏｎｓｏｆｃｏｍｍｅｒｃｉａｌＡＢ5 ｔｙｐｅａｌｌｏｙｓａｒｅＭｍＮｉ3.5 5 Ｃｏ0 .75 Ｍｎ0 .4Ａｌ0 .3ａｎｄＭＩＮｉ3.5 5 Ｃｏ0 .75 Ｍｎ0 .4Ａｌ0 .3(ＭＩ :Ｌａｎｔｈａｎｕｍ ｒｉｃｈｍｉｓｃｈｍｅｔａｌ,Ｍｍ :Ｃｅｒｉｕｍ ｒｉｃｈｍｉｓｃｈｍｅｔａｌ ) .Ｉｔｉｓｗｅ…     

贮氢合金V3TiNi0.56Al0.2的电化学性能

以NH4VO3、Al等为原料采用自蔓延高温法制备了钒基固溶体型贮氢合金V3TiNi0.56Al0.2,研究了V3TiNi0.56Al0.2贮氢合金的组织结构和电化学性能。结果表明:铸态贮氢合金V3TiNi0.56Al0.2的最大放电容量为350 mA.h/g,活化性能较好,但氢的扩散系数小,循环性能和高倍率放电能力差。合金失去活性的原因是循环过程中钒基固溶体主相不断溶解到电解液中,通过真空熔炼处理可以改善合金的循环性能和高倍率放电性能。     

Electrochemical hydrogen storage properties of La0.95Mg2.05Ni9 alloy prepared by mechanical alloying

1　INTRODUCTIONTheMg basedhydrogenstoragealloysastheac tivematerialsofmetalhydrideelectrodeshaveattract edattentionbecauseofhighertheoreticalcapacitiesforhydrogenabsorption/desorption ,andthelowerpricecomparedwiththeotherhydrides[17] .Recent ly ,thecharge dischargepropertiesofMg basedalloysatroomtemperaturehavebeengreatlyimprovedbysomeresearchers[813] .Inparticular ,theMg Ni REsystemalloyisoneofthemost promisinghydrides[14 16 ] .Tanakaetal[15] reportedthatthenanocrystallineMg Ni RE(R…     

温度对La-Mg-Ni-Co-Mn贮氢电极合金电化学性能的影响

系统研究了温度对La07Mg03Ni2875Co0.525Mn0.1贮氢合金电化学性能尤其是电化学动力学性能的影响.结果表明:La07Mg03Ni2 875Co0525Mn0,合金由(La,Mg)Ni3相和LaNi5相构成.合金的最大放电容量随着温度升高从-20℃时的277.5 mAh/g增加到30℃时的406.2 mAh/g.随着温度升高,合金放电平台电位逐渐变负,放电过电位逐渐减小,合金电极的极化减弱.高倍率性能、交换电流密度、氢的扩散系数研究表明合金的电化学动力学性能随着温度升高不断提高.该合金的氢扩散活化能为17.6 KJ/mol.     

Influence of material processing on crystallographic and electrochemical properties of cobalt-free LaNi4.95Sn0.3 hydrogen storage alloy

1 Introduction Mischmetal-based AB5-type alloys containing about 10% Co (mass fraction) are now widely used as the negative electrode materials of Ni/MH batteries because of their long cycle life and good overall properties. It is known that Co is an ess…     

贮氢合金制备工艺对其电化学性能的影响

AB5型贮氢合金是目前国内外MH／Ni电池生产中是耿广泛的负极材料，而贮氢合金的电化学性能是由合金的成分，微观结构和表面状态决定的，本文综述了AB5型贮氢合金制备工艺－熔炼，热处理以及制粉工艺对其化学性能的影响，指出制备工艺对贮氢合金的成分均匀性和微观结构影响很大，而提高贮氢合金电化学性能最有效的方法是通过合金成分优化和采用较优的制备工艺，来获得高容量，长寿命，低价格的贮氢合金。     

Al对无钴AB5型贮氢合金微观结构和电化学性能的影响

采用单辊快凝方法制备了过化学计量比稀土贮氢合金La(NiMn)α-xAlx(5<α<6,x为0~0.5),研究了Al含量及淬速对合金电极性能及微观结构的影响。结果表明:快淬过化学计量比合金相结构均为过饱和CaCu5型单相,且随Al含量的增加,合金晶胞体积呈线性增大;不同淬速条件下合金凝固组织的形貌和晶态存在明显差别。随Al含量的增加,合金电极的放电容量有所降低,但电极循环寿命得到极大改善。当x=0.3和淬速为10~15 m/s时,合金电极的最大放电容量为322和309 mA.h/g,经150次循环后,电极容量保持率分别为93.5%和95.5%。低温(400℃)退火对合金电极活化性能有所改善,但并未影响合金的循环寿命。     

Relationship between cooling rate and electrochemical performance of melt-spun AB_5 alloy

1　INTRODUCTIONNi/MHsecondarybatterieshaverapidlybeendevelopedandgraduallysubstitutedforNi/Cdbatter iesintherecentdecadeduetoitshighspecificenergydensityandhavingnopoisonouselementcadmium .TheactivematerialofnegativeelectrodewidelyusedinNi/MHsecondarybatteriesisAB5 typehydrogenstoragealloynowadays .However ,itisstillneededtoimprovethecomprehensive propertiesofAB5 typehydrogenstoragealloyforprolongingtheservicelifeofNi/MHbatteries .Anormalmethodtoimprovethecomprehensivepropertiesofthe…     

Design of Zr-based AB_2 type hydrogen storage alloys

1　INTRODUCTIONPresently ,therearetwokindsofhydrogenstor agealloys (AB5andAB2 )usedinnickel metalhy dride (Ni/MH)battery .AB2 typehydrogenstoragealloyhasworseactivationperformanceandlowerini tialcapacitythoughitscapacityishigherandlifeislongerthanAB5alloy .Atthesametime ,AB2 typehydrogenstoragealloyismoreexpensivethanAB5typehydrogenstoragealloy .AlltheaboveaspectsembarrasstheactualapplicationofAB2 typehydrogenstoragealloy .PropertiesofAB2 typehydrogenstor agealloy ,suchascapacity ,…     

V2O5修饰AB5储氢合金的性能研究

用不同量的V2O5对双辊快淬法制AB5型合金La0.65Ce0．28Pr0.02Nd0.05Ni3.8Co0．7Mn0.3Al0.2进行球磨修饰，得到V2O5修饰量分别为0％，3％，6％，10％（质量分数）的4个试样。对试样进行激光粒度分析、X射线衍射物相组成分析、扫描电子显微镜微观形貌观察，用恒电流充放电研究了试样作为镍氢电池负极时的性能，用循环伏安法研究了氧化还原氢动力学性能。结果表明，V2O5修饰使合金颗粒细化，但是主相合金依然保持了单一的六方晶系的CaCu5型结构。修饰V2O5使合金的实际放电容量得到提高，最高达到332．6mAh/g，合金电极表面的氢氧化还原过程动力学性能得到改善，修饰V2O5对电极反应有催化作用，同时合金的倍率放电性能得到明显改善。     

Low-temperature performance and high-rate discharge capability of AB5-type non-stoichiometric hydrogen storage alloy

Low-temperature performance and high-rate discharge capability of AB5-type non-stoichiometric hydrogen storage are studied. X-ray diffraction（XRD）, pressure-composition-temperature（PCT） curves and electrochemical impedance spectroscopy（EIS） are applied to characterize the electrochemical properties of ABx （x=4.8, 4.9, 5.0, 5.1, 5.2） alloys. The results show that the non-stoichiometric alloys exhibit better electrochemical properties compared with that of the AB5 alloy.     

AB_5型贮氢合金电极添加Co_3O_4的电化学性能

将不同含量的Co3O4（2%,4%,6%,8%,质量分数）作为添加剂加入到储氢合金中,采用机械混合法进行改性处理。对添加Co3O4的合金电极的电化学性能和电极过程进行研究。结果表明：放电容量有了较大增加,添加2%、4%、6%、8%Co3O4的电极放电容量比空白电极容量分别增加0.83%,4.86%,7.18%和9.21%。线性极化曲线和电化学阻抗谱测试表明,添加Co3O4降低了电极的电荷转移电阻。循环伏安、扫描电镜和EDS测试表明,添加的Co3O4可部分溶解,发生Co-Co（OH）2可逆氧化？还原反应,从而改善储氢合金的电化学性能。     

Hydrogen storage properties of non stoichiometric AB_2-type metal hydride

1　ＩＮＴＲＯＤＵＣＴＩＯＮＴｉｂａｓｅｄｈｙｄｒｏｇｅｎｓｔｏｒａｇｅａｌｌｏｙｓｂｅｃａｍｅａｔｔｒａｃｔｉｖｅｂｅｃａｕｓｅｏｆｔｈｅｉｒｌａｒｇｅｈｙｄｒｏｇｅｎｃａｐａｃｉｔｉｅｓ.Ｂｅｒｎａｕｅｒｅｔａｌ[1]ａｎｄＬｉｅｔａｌ[2]ｐｏｉｎｔｅｄｏｕｔｔｈａｔｍｕｌｔｉｅｌｅｍｅｎｔＴｉｂａｓｅｄｈｙｄｒｏｇｅｎｓｔｏｒａｇｅａｌｌｏｙｓａｒｅｍｏｒｅｐｒｏｍｉｓｉｎｇｍａｔｅｒｉａｌｓｆｏｒｐｒａｃｔｉｃａｌａｐｐｌｉｃａｔｉｏｎｓ.(ＴｉＺｒ)(ＭｎＣｒＶＦｅ)2ａｌｌｏｙｉｓａｃｏｍｍｏｎ…     

Effect of rolling processing on microstructure and electrochemical properties of high active aluminum alloy anode

The effect of rolling processing on the microstructure,electrochemical property and anti-corrosion property of Al-Mg-Sn-Bi-Ga-In alloy anode in alkaline solution(80℃,Na2SnO3+5 mol/L NaOH)was analyzed by the chronopotentiometry (E-T curves),hydrogen collection tests and modern microstructure analysis.The results show that when the rolling temperature is 370℃,the electrochemical activity of Al anode decreases gradually with the increase of pass deformation in rolling,while the anti-corrosion property is improved in the beginning and then declined rapidly.When the pass deformation of rolling is 40%,the Al anode has good electrochemical activity as good as the anti-corrosion property and with the increase of rolling temperature,both electrochemical activity and anti-corrosion property of Al anode increase first and then decrease.When the rolling temperature is 420 ℃,the aluminum alloy anode has the most negative electrode potential of about-1.521 V(vs Hg/HgO)and the lowest hydrogen evolution rate of 0.171 6 mL/(min·cm2).The optimum comprehensive performance of Al alloy anode is obtained.