铸态及快淬态无钴AB5型贮氢合金的循环稳定性

对AB5型LaxMm1-x(NiMnSiAlFe)49(x=0,0.45,0.75,1.00,摩尔分数)贮氢合金进行了快淬处理,研究了La含量及快淬工艺对合金微观结构及电化学循环稳定性的影响.结果表明:La含量的增加对铸态合金的循环稳定性没有明显影响,但使快淬态合金的循环稳定性下降,且快淬处理能显著提高合金的循环稳定性.当La替代量从0增加到1.00时,经300次充放循环后,铸态合金的容量保持率(Rh)从59.2%增加到59.8%;16 m/s淬速快淬态合金的容量保持率从83.9%下降到65.0%.对于x=0.45的合金,当淬速从0(铸态被定义为淬速等于0)增加到28 m/s时,容量保持率从59.8%增加到75.8%.     

钐对无钴AB5型稀土贮氢合金微观结构和电化学性能的影响

用真空感应熔炼铸锭以及快淬工艺制备过化学计量比无钴AB5型稀土贮氢合金La0.85-xCe0.15 SmxNi4.55 Mn0.40Al0.30和La0.69Ce0.31-xSmxNi4.55Mn0.40Al0.30(x=0,0.08,0.16).研究了钐含量及快淬对无钴AB5型稀土贮氢合金的微观结构、吸放氢性能、电化...     

Photoelectrochemical characteristics of AB5-type hydrogen storage alloy modified with SrTiO3 photocatalyst

Perovskite-type SrTiO3 powders were prepared by using strontium acetate, tetrabutyl titanate and sodium hydroxide via direct hydrolysis-precipitatlon process. AB5-type hydrogen storage alloy（HSA） electrodes modified with SrTiO3 powders were prepared and the photoelectrochemical characteristics of the as-prepared electrodes were investigated. The results of cyclic voltammograph show that the current of reduction peak increases remarkably under the light irradiation. The obvious photochargeable properties are obtained for the hydrogen storage alloys modified with Perovskite-type SrTiO3 powders. During photocharging process, the potential of the electrode shifts quickly to negative direction and a potential plateau occurs. HSA electrode modified with SrTiO3 powders prepared by direct hydrolysis-precipitation process gives the higher potential of about -0.90 V（vs Hg/HgO） under the light irradiation. SEM observation discloses that a large amount of microcracks occur on the surface of the electrode after photocharging process, which is caused by the formation of hydride in the bulk of electrode.     

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.     

退火处理对MlNi4.0Al0.3Si0.1Fe0.6无Co储氢电极合金的微结构和电化学性能的影响

研究了退火处理(1.173～1.273.K、 3.h)对无Co贮氢合金MlNi4.0Al0.3Si0.1Fe0.6的微结构和电化学性能的影响. XRD分析表明, 退火态合金仍为单相CaCu5型结构, 但合金相的成分和结构的均匀性得到明显改善. 金相观察和能谱分析显示: 铸态合金为比较粗大的树枝晶结构并存在明显的成分偏析; 经1.173.K处理后的合金仍为树枝晶, 且树枝结构更为明显; 但经1.223～1.273.K处理后合金的显微组织转变为等轴晶; 退火处理使合金中元素的分布趋于均匀化. 电化学测试表明, 退火处理后合金的放电容量有所提高, 循环稳定性得到显著改善, 但高倍率放电性能略有降低. 研究发现, 退火态合金电极的交换电流密度及氢在合金中的扩散系数较铸态合金的有所减小是导致其高倍率放电性能降低的主要原因.     

添加Si对A_2B_7型电极合金结构及电化学贮氢性能的影响(英文)

为改善La–Mg–Ni系A2B7型合金的电化学贮氢性能,在合金中添加一定量的Si元素,通过真空熔炼及退火处理的方法制备La0.8Mg0.2Ni3.3Co0.2Six(x=0-0.2)电极合金。研究Si元素的添加对合金结构及电化学贮氢性能的影响。结果表明,铸态及退火态合金均为多相结构,分别为Ce2Ni7型的(La,Mg)2Ni7相和CaCu5型的LaNi5相以及少量的残余相LaNi3。Si元素的添加没有改变合金的主相,但使得合金中的(La,Mg)2Ni7相减少而LaNi5相增加。添加Si显著地影响了合金的电化学性能。随着Si含量的增加,铸态及退火态合金的放电容量逐步降低,但循环稳定性却随着Si含量的增加而增强。此外,合金电极的高倍率放电性能、极限电流密度、氢扩散系数以及电化学交流阻抗谱的测试均表明合金的电化学动力学性能随着Si含量的增加先增加而后减小。     

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.     

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.     

Effect of Manganese substitution on hydrogen storage properties of LaNi4.25-xAl0.75Mnx alloy

The effect of Mn substitution on phase structure, hydrogen hydriding/dehydriding properties (plateau pressure and slope) and reaction heat enthalpy of LaNi4.25-xAl0.75Mnx alloys (x=0, 0.25, 0.35, 0.45, 0.55 and 0.65) were studied.The experimental results show that all LaNi4.25-xAl0.75Mnx alloys have single phase and have the same hexagonal structure as that of LaNi5 alloy (CaCu5 type, P6/mmm).With increasing Mn substitution content, the cell parameters of LaNi4.25-xAl0.75Mnx alloy greatly increase, but the maximum hydrogen storage capacity and the equilibrium absorption pressure of LaNi4.25-xAl0.75Mnx alloy decrease from 1.38 wt.% to 1.18 wt.% and from 1.61 to 0.0712 MPa, respectively.Moreover, the hydrogen pressure plateau slope factor σ increases from 0.014 to 0.18, but the hysteresis factor is nearly constant.The heat enthalpy absolute value |ΔHplat| increases from 46.7 kJ·mol-1 H2 to 56.1 kJ·mol-1 H2 as the Mn content x increases from 0 to 0.65.     

退火热处理对TiMn基储氢合金结构及性能的影响

通过压力—组成—温度曲线、放氢量测试及X射线衍射研究了退火热处理对TiMn基储氢合金结构及性能的影响。结果表明，退火热处理能明显改善储氢合金的活化性能，在一定程度上提高吸放氢性能，降低吸放氢反应的焓变。XRD分析表明，热处理后储氢合金的相组成由单一的γ—TiMnl-2转变为γ—TiMnl—2和六方TiMn5相共存。     

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.     

Pr替代Ti对TiFe系储氢合金微观结构和电化学性能的影响

采用感应熔炼法制备Ti1.1-xPrxFe0.6Ni0.3Mn0.2(x = 0,0.04,0.06,0.08)合金,通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、蓝电电池测试等手段对合金的显微组织结构和电化学性能进行分析.XRD结果表明:合金基体相为TiFe,以及少量的ZrMn2第二相,添加Pr未改变合金相组...     

Effect of Ni on Mg based hydrogen storage alloy Mg3Nd

Magnesium-neodymium based alloys were prepared by induction melting in an alumina crucible under protection of pure argon atmosphere. XRD patterns show that the as-melted Mg-Nd and Mg3NdNi 0.1 diffraction peaks can be excellently indexed with D03 structure (BiF3 type, space group Fm3m ). The lattice constant of Mg3Nd phase is 0.7390 nm, which is determined by XRD analysis using Cohen's extrapolation method. The reversible hydrogen storage capacity reaches 1.95wt.% for Mg3Nd and 2.68wt.% for Mg3NdNi0.1 . The desorption of hydrogen takes place at 291 ℃ for Mg3Nd and at 250 ℃ for Mg3NdNi 0.1 . The alloys could absorb hydrogen at room temperature with rapid hydriding and dehydriding kinetics after only one cycle. The enthalpy (ΔH ) and entropy (ΔS ) of Mg3Nd-H dehydriding reaction were -68.2 kJ·mol-1 H2 and -0.121 kJ·(K·mol)-1 H2 determined by using van't Hoff plot according to the pressure-composition-isotherms (P-C-I) curve measured at different temperatures. Hydrogen absorption kinetic property of Mg3NdNi 0.1 alloy was also measured at room temperature.     

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。     

Nd替代La对La-Mg-Ni系A2B7型贮氢电极合金性能的影响

用冷坩锅磁悬浮熔炼方法制备了La0.7-xNdxMg0.3(NiCoAl)3.5(x=0,0.1,0.3,0.5,0.7)贮氢电极合金,采用X射线衍射Rietveld法、三电极体系及扫描电镜研究合金的相结构和电化学性能以及电极的表面状态。Rietveld法分析表明:合金为多相结构,主相均为Ce2Ni7型六方相,还包括CaCu5型六方相、PuNi3型菱方相、MgCu2型立方相及CrB型正交相;且随着Nd含量x的增加,主相含量增加,相应CaCu5型和MgCu2型相含量降低,PuNi3型相含量则在一定范围内波动;且各组成相单胞体积均呈线性降低趋势。p—c—t曲线显示,合金放氢平台区域变窄,平台压力升高,平台先稍有倾斜后逐渐平坦。电化学性能测试显示,最大放电容量基本呈线性递减;活化性能优异;高倍率放电性能先提高后稍有降低;循环稳定性得到改善。     

Electrochemical properties of AB5 type hydrogen storage alloy as anode electrocatalyst of PEMFC

1　INTRODUCTIONIn recent years, the application of the roomtemperature type ( < 100 ℃) polymer electrolytemembrane fuel cells(PEMFCs) as a primary powersource in electric vehicles and portable equipmentsetc has received increasing attention[1 4]. Usuallyin a PEMFC system, platinum is chosen as the e lectrode electrocatalyst, however, it results in ahigh cost PEMFC system for commercialization be cause Pt is a high cost, source limit metal. So,looking fo…     

Hydrogen storage properties of non stoichiometric AB_2-type metal hydride

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

粉末粒度对AB5型合金电化学性能的影响

研究了粉末粒度对AB5型储氢合金电化学性能的影响.结果表明当合金粉末粒度为22.49～163.8 μm时,随粉末粒度的减小,储氢合金电极的电化学容量降低;由于粉末粒度大的电极负极充放电循环寿命的衰减率小于粉末粒度小的衰减率,所以随粉末粒度的减小,储氢合金电极材料充放电循环寿命缩短.     

Al对La—Mg-Ni系贮氢合金电极电化学性能的影响

采用固相扩散法制备La0.7Mg0.3Ni3.5-xAlx(x=0,0.1,0.3,0.7,1.0)和La0.7Mg0.3Ni2.8Co0.7-xAlx(x=0,0.1,0.2,0.3,0.4)贮氧合金,采用X射线衍射、能谱分析及循环伏安等方法分析含金的相结构和电极电化学性能,研究元素Al替代对合金电化学性能的影响.结果表明:合金由LaNi5、La2Ni7和LaNi3三相组成,随着Al替代量的增加,La2Ni7相晶胞逐渐膨胀,LaNi5相大量减少,LaNi3相增加,La2Ni7相有利于合金电化学性能的提高,然而过高的Al含量会对合金的放电性能带来不利影响.La0.7Mg0.3Ni3.4Al0.1和La0.7Mg0.3Ni2.8Co0.6Al0.1合金电极的最大放电容量分别为354.5 mA·h/g和373.1 mA·h/g.循环伏安测试显示较明显的氧化峰和还原峰,且峰电位差较小,反映合金电极较好的吸放氢反应可逆性.     

淬火温度对Nd1.5Mg0.5Ni7储氢合金相结构的影响

通过对不同温度淬火的Nd₂Ni₇和Nd_1.5Mg_0.5Ni₇样品粉末进行X射线衍射分析(XRD)和扫描电子显微镜/能谱分析(SEM/EDS),研究了Nd_1.5Mg_0.5Ni₇合金淬火后的相结构。结果表明,淬火后,Nd_1.5Mg_0.5Ni₇三元合金主要由Ce₂Ni₇型相和Gd₂Co₇型相组成;淬火温度对合金主相晶格常数几乎没有影响;Mg的加入促进了低温相的形成,并减少了杂质相的生成。