元素掺杂对镁基储氢合金电化学性能的影响

利用氢化燃烧合成复合高能球磨法制备镁基储氢电极合金Mg2NiH4,并对合金进行不同元素(Cr、Co、Nb、Ti和V)掺杂处理。使用X线衍射仪(XRD)和电化学工作站对材料结构性能进行表征,并考察不同元素掺杂对电极合金的结构和电化学性能的影响。结果表明:少量金属元素掺杂处理并没有改变合金的主相结构。元素掺杂降低了合金电极的最大放电容量和动力学性能,但是合金电极的电化学循环稳定性均得到不同程度的提高,其中Ti掺杂处理对于改善合金电极电化学循环性能最为明显。     

La0.7Mg0.3Ni3.4-x(Al0.3Co0.4)0.2+x(x=0~0.3)合金电极电化学性能研究

在氩气保护下,采用悬浮熔炼法制备La0.7Mg0.3Ni3.4（Al0.3Co0.7）x（x=0,0.2,0.4,0.6）储氢合金,用X射线衍射仪测试相组成,并用MDI Jade 5.0软件分析相组成和晶胞参数,用开口三电极法测试电极电化学性能。结果表明,合金相主要由LaNi5、LaMg2Ni9、La2Ni7和LaNi2.28相组成,随着合金中Al和Co含量的增加,合金放氢平台压下降,最大吸氢量为1.43%（x=0）,合金电极最大放电容量Cmax为381mA.h.g-1（x=0）,合金电极100个充放循环后的容量保持率S100从53.0%（x=0）增加到57.1%（x=0.3）,循环稳定性增强。当x=0.1时,合金电极的电化学动力学性能较好。     

导电剂镍粉对La0.7Mg0.3Ni2.6Co0.7合金电极电化学性能的影响

采用放电容量、循环寿命、伏安特性、高倍率放电、交流阻抗等方法研究不同导电剂镍粉含量对La0.7Mg0.3Ni2.6Co0.7合金电极电化学性能的影响。结果表明:La0.7Mg0.3Ni2.6Co0.7+xwt%Ni(x=0.0,5.0,7.5,10.0,12.5)合金电极的放电容量分别为388.0、410.7、409.6、412.2、421.3 mAh/g,高倍率放电性能HRD1200从40.2%(x=0.0)增大到75.7%(x=12.5),同时合金电极的电荷转移阻抗明显降低,添加导电剂镍粉有利于电流在电极中分布趋于均匀化,增大了活性物质的填充量,促使合金电极的放电容量增加。电荷转移阻抗的降低有利于氢原子在合金内部扩散,从而有效地改善合金电极的高倍率放电性能。     

烧结温度对La-Mg-Ni系储氢合金的相结构与电化学性能的影响

采用粉末烧结法制备La0.7Mg0.3Ni2.8Co0.5合金,并系统研究1173和1273 K下Ar保护分别烧结12 h所制备合金的微观结构与电化学性能。结果表明:合金均由(La,Mg)Ni3和LaNi52种主相所构成,1173 K条件下却含有少量MgNi2相,而1273 K条件下所制备的合金相结构中不含MgNi2相,这说明高温条件较有利于合金的合成。高温条件下所制备的合金具有较高的放电容量,且循环稳定性和高倍率放电性能均有明显的提高,电化学动力学也随制备温度的增高而改善。     

Effect of stoichiometry and Cu-substitution on the phase structure and hydrogen storage properties of Ml-Mg-Ni-based alloys

To improve the electrochemical properties of rare-earth-Mg-Ni-based hydrogen storage alloys, the effects of stoichiometry and Cu-substitution on the phase structure and thermodynamic properties of the alloys were studied. Nonsubstituted Ml_0.80Mg_0.20(Ni_2.90Co_0.50-Mn_0.30Al_0.30)_x (x=0.68, 0.70, 0.72, 0.74, 0.76) alloys and Cu-substituted Ml_0.80Mg_0.20(Ni_2.90Co_0.50-y Cu_y Mn_0.30Al_0.30)_0.70 (y=0, 0.10, 0.30, 0.50) alloys were prepared by induction melting. Phase structure analysis shows that the nonsubstituted alloys consist of a LaNi₅ phase, a LaNi₃ phase, and a minor La₂Ni₇ phase; in addition, in the case of Cu-substitution, the Nd₂Ni₇ phase appears and the LaNi₃ phase vanishes. Thermodynamic tests show that the enthalpy change in the dehydriding process decreases, indicating that hydride stability decreases with increasing stoichiometry and increasing Cu content. The maximum discharge capacity, kinetic properties, and cycling stability of the alloy electrodes all increase and then decrease with increasing stoichiometry or increasing Cu content. Furthermore, Cu substitution for Co ameliorates the discharge capacity, kinetics, and cycling stability of the alloy electrodes.     

La0.7Mg0.3-xCaxNi2.5Co0.5(x=0～0.15)储氢合金的放电容量衰退机理研究

采用感应熔炼结合粉末烧结两步法制备了La_(0.7)Mg_(0.3-x)Ca_xNi_(2.5)Co_(0.5)(x=0～0.15)储氢合金,并对合金的放电容量衰退机理进行了研究.研究结果显示随着Ca含量的增加,合金的相结构没有发生明显变化,只是晶胞参数逐渐增大,即Ca主要替代了超晶格结构AB2结构单元中的Mg,但在AB5结构单元中少量的Ca恰恰对合金的放电容量产生了重要的影响.Ca在AB2和AB5两种结构单元中的存在会降低储氢过程中晶胞内部的膨胀应力,Ca的溶解能够抑制Mg的腐蚀,生成微溶于水的腐蚀产物,并提高了合金表面具有催化活性的Ni含量,改善了合金的循环寿命.较高的Ca含量会严重破坏合金的相结构,生成过量的腐蚀产物因不能完全溶于水而在合金表面形成包覆层,阻碍了电极反应,造成合金循环过程中放电容量的急剧下降.     

热处理对贮氢电极合金La0.7Mg0.3Ni2.45Co0.75Mn0.1Al0.2的微结构与电化学性能的影响

研究了热处理时间对贮氢电极合金La0.7Mg0.3Ni2.45Co0.75Mn0.1Al0.2的微结构与电化学性能的影响。XRD分析结果表明,所有合金均由(La,Mg)Ni3与LaNi5两相构成,热处理并没有使该贮氢合金发生相变。电化学研究结果表明,随着热处理时间的延长,合金电极的最大放电容量与循环稳定性能均得到明显改善,而高倍率放电性能却逐渐恶化。     

La0.7Zr0.1Mg0.2Ni3.4-xCoxFe0.1合金的制备与电化学性能研究

在氩气保护下采用电磁感应熔炼制备La0.7Zr0.1Mg0.2Ni3.4-xCoxFe0.1（x=0.15,0.25,0.35,0.45）合金,研究合金的相结构,以及Co元素部分取代Ni元素对合金的气态储氢性能和电化学性能的影响。结果表明,合金主要由LaNi5、LaNi2以及La2MgNi9相组成。合金电极的最大放电容量分别为346.7mAh/g（x=0.15）、320.3mAh/g（x=0.25）、363.0mAh/g（x=0.35）和313.3mAh/g（x=0.45）,经过65个充放电循环后,合金电极的容量保持率从63.0%（x=0.15）增加到80.2%（x=0.35）,然后再下降到75.0%（x=0.45）。La0.7Zr0.1Mg0.2Ni3.15Co0.25Fe0.1合金具有较高的高倍率放电性能（HRD1200%=67.3）和较大的极限电流密度（IL=386.8 mA/g）,显示出其良好的电化学动力学性能。     

添加硼对La-Mg-Ni系(PuNi3-型)贮氢合金微观结构及电化学性能的影响

为了提出La-Mg-Ni(PuNi3型)系贮氢合金的电化学循环稳定性,在La2Mg(Ni0.85Co0.15)9合金中添加微量的B,用铸造及快淬工艺制备La2Mg(Ni0.85Co0.15)9Bx(x=0,0.05,0.10,0.15,0.20)贮氢合金,分析测试铸态及快淬态合金的微观结构与电化学性能,研究硼对合金微观结构及电化学性能的影响。结果表明:铸态合金具有多相结构,包括主相(La,Mg)Ni3相(PuNi3型)和LaNi5相,一定量的LaNi2相和微量的Ni2B相经快淬处理后,Ni2B相消失,且其他相的相对量随淬速的变化而变化。硼的加入提高了铸态及快淬态合金的循环稳定性,但使铸态合金的容量下降;铸态合金的电化学容量随B含量的增加单调下降,而快淬态合金的容量随B含量的增加有一极大值,B对铸态及快淬态合金电化学性能的影响机理是完全不同的。     

Hydrogen storage and low-temperature electrochemical performances of A2B7 type La-Mg-Ni-Co-Al-Mo alloys

The effect of Mo-addition on hydrogen storage and low-temperature electrochemical performances of La-Mg-Ni-Co-Al alloys is investigated. The alloys were synthetized via vacuum induction melting followed by annealing treatment at 1123 K for 8 h. The major phases in the annealed alloys are consisted of (La, Mg)2Ni7, (La, Mg)5Ni19 and LaNi5 phases. Mo-addition facilitates phase transformation of LaNi5 into (La, Mg)2Ni7 and (La, Mg)5Ni19 phases. Hydrogen absorption/desorption PCI curves indicates that the hydrogen storage capacity of the alloy increases remarkably with the addition of Mo. Furthermore, the La0.75Mg0.25Ni3.05Co0.2Al0.05Mo0.2 alloy shows excellent hydriding/dehydriding kinetics with a higher capacity, requiring only 100 s to reach its saturated hydrogen capacity of 1.58 wt% at low temperature of 303 K, and releasing 1.57 wt% hydrogen within 400 s at 338 K. Electrochemical experiments manifest that the Mo-added alloy electrode has perfect activation properties and the maximum discharge capacity. The low-temperature dischargeability shows that the La0.75Mg0.25Ni3.05Co0.2Al0.05Mo0.2 alloy exhibits the excellent low-temperature discharge performance, and the maximum discharge capacity is improved from 231.0 to 334.6 mAh/g at 253 K. The HRD property of the alloy electrode is enhanced, suggesting that Mo enhances the kinetic ability at low-temperature.