Novel progress in the development of hydrogen storage materials

A new dehydrogenation mechanism for LiBH4, a new hydrogen storage material, has recently been

Cycling hydrogen desorption properties and microstructures of MgH_(2)-AlH_(3)-NbF_(5) hydrogen storage materials

Magnesium hydride(MgH_(2)) is a candidate material for hydrogen storage.MgH_(2)-AlH_(3) composite shows superior hydrogen desorption properties than pure MgH_(2).However,this composite still suffers from poor cycling performance.In this work,NbF_(5) was utilized to improve the cycling properties of the MgH_(2)-AlH_(3) composite.Cycling hydrogen desorption studies show that NbF_(5) significantly improves the cycling stability of MgH_(2)-AlH_(3).The MgH_(2)-AlH_(3)-NbF_(5) composite can release about 2.7 wt% of hydrogen at 300℃ for 1 h and the hydrogen desorption capacity can maintain at 2.7 wt% for more than100 cycles.In comparison,the hydrogen desorption capacity of the MgH_(2)-AlH_(3) composite is decreasing with the cycle number increasing.The capacity is reduced from a maximum value of 3.3 wt% to about 1.0 wt% after 40 cycles.Brunauer-Emmett-Teller(BET) surface area measurements show that the particle size of MgH_(2)-AlH_(3) composite decreases after cycling,which means pulverization of the composite.NbF_(5) can to some extent suppress the pulverization of the composite during cycling,which partially contributes to the improvement of the cycling hydrogen desorption properties of the material.

Influence of material processing on crystallographic and electrochemical properties of cobalt-free LaNi_(4.95)Sn_(0.3) hydrogen storage alloy

The effects of the alloy preparation methods, including the conventional casting, annealing and melt-spinning, on the crystallographic and electrochemical properties of the Co-free LaNi4.95Sn0.3 alloy samples were investigated. The results reveal that the as-cast alloy consists of a main phase of CaCu5-type structure and a little second phase (Sn) with noticeable composition segregation and rather poor cycling stability (S200=40.1%). While the annealed and melt-spun alloys are of single CaCu5-type structure phase with a more homogeneous composition and lower cell volume expansion rate (?V/V) on hydriding, and a dramatically improved cyclic stability (S200=73.6%?76.2%), although their activation rate, initial capacity and high-rate dischargeability are lowered somewhat. It is found that the decrease in both the electrocatalytic activity and the hydrogen diffusion rate of the annealed and melt-spun alloys is the main cause for their relatively lower high-rate dischargeability, and the improved cycling stability is due to their lower volume expansion on hydriding and more uniform composition.

Effects of Strip Casting and Annealing on Electrochemical Properties of LPCNi_(3.55)Co_(0.75)Mn_(0.4)Al_(0.3) Hydrogen Storage Alloys

The effect of thickness (1 similar to 10 mm) of the ingots on the electrochemical properties of as-cast and annealed strip cast LPCNi3.55Co0.75Mn0.4Al0.3 hydrogen storage alloys was investigated. It is found that the 0.2 C discharge capacity of as-cast LPCNi3.55Co0.75Mn0.4Al0.3 alloy increases with the increase of the thickness of the ingots. As-east alloy with the thickness of 10 mm shows better activation property, higher 1C discharge capacity and better cyclic stability than others. It is mainly contributed to its larger unit cell volume and less internal stress. Annealed LPCNi3.55Co0.75Mn0.4Al0.3 alloy with the thickness of 3 mm shows much better comprehensive electrochemical properties than as-east one; The cyclic. stability of the alloy with the thickness of 6 mm and the activation properties of the alloys with the thickness of 3 similar to 6 mm are improved after annealing. It is mainly owing to the great release of internal stress and the decrease of the segregation of Mn in the alloys.

Catalytic effect of Ni@rGO on the hydrogen storage properties of MgH2

Uniform-uispersed Ni nanoparticics(NPs)anchored on reduced graphene oxide(Ni@rGO)catalyzed MgH2(MH-Ni@rGO)has been fabricated by mechanical milling.The effects of milling time and Ni loading amount on the hydrogen storage properties of MgH2 have been investigated.The initial hydrogen desorption temperature of MgH2 catalyzed by 10 wt.%Ni4@rGO6 for milling 5 h is significantly decreased from 251℃ to 190℃.The composite can absorb 5.0 wt.%hydrogen in 20 min at 100℃,while it can desorb 6.1 wt.%within 15 min at 300℃.Through the investigation of the phase transformation and dehydrogenation kinetics during hydrogen ab/desorption cycles,we found that the in-situ formed Mg2Ni/Mg2NiH4 exhibited better catalytic effect than Ni.When Ni loading amount is 45 wt.%,the rGO in Ni@rGO catalysts can prevent the reaction of Ni and Mg due to the strong interaction between rGO and Ni NPs.

Microstructure and electrochemical properties of LaNi_(4-x)FeMn_x (x=0-0.8) hydrogen storage alloys

In order to reduce the cost of LaNi5 based hydrogen storage alloys, effect of substitution of Mn for Ni on structural and electrochemical properties of LaNi4-xFeMnx (x=0-0.8) hydrogen storage alloys was studied systematically. X-ray diffraction (XRD) and scanning electron microscope (SEM) showed that LaNi5 and La2Ni7 phases were invariably present in all alloy samples, and when x >= 0.4, (Fe, Ni) phase was observed. Electrochemical studies revealed that the discharge capacity reached a maximum value of 306.4 mAh/g when x=0.2 and the cycling stability decreased with the increase of x. With the increase of Mn content, hydrogen diffusion coefficient decreased, whereas high rate discharge-ability (HRD) and exchange current density first increased slowly when x <= 0.2 and then decreased markedly when x=0.8, indicating that electrochemical reaction on the surface of alloy electrodes had strong influence on kinetic property.

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

A new type of AB_5-x%LaMg_3(x=2, 3, 4, 5, 6, 7, 8)composite hydrogen storage alloys were prepared by sintering the powder mixtures of a commercial AB_5 alloy and LaMg_3 alloy. The phase structure and electrochemical characteristics of the composite hydrogen storage alloys were also studied. It is shown that AB_(5)-x%LaMg_3(x=2, 3, 4, 5, 6, 7, 8)composites have mult; phase structure. The matrix phase has CaCu_5 structure, the second phase is LaNi_3 phase. The maximum discharge capacity, discharge capacity at low temperature and HRD of AB_5 alloy electrodes are greatly improved after the composite. The maximum discharge capacity of the composite electrodes increases from 325 mAh·g^(-1) for x=0 to 358 mAh·g^(-1) for x=5, and the HRD of the composites for x=5 at the current density of 1200 mA·g^(-1)30% of that of the alloy at 60 mA·g^(-1). The discharge capacity of AB_5-x%LaMg_3 composite alloy electrode at 233 K is up to 174 mAh·g^(-1). The improvement of the electrochemical characteristics of the composite electrodes seems to be related with formation of the LaNi_3 second phase.

Enhanced dehydrogenation kinetic properties and hydrogen storage reversibility of LiBH_4 confined in activated charcoal

LiBH4 was confined into activated charcoal（AC） by melt infiltration method（MI）, and its effects on the hydrogen sorption properties were investigated. The N2 adsorption results reveal that melt infiltration method can effectively incorporated LiBH4 into AC. It can maintain the structural integrity of the scaffold and ensure the confinement effect. The nano-confined LiBH4/AC starts to release hydrogen at around 190 °C, which is 160 °C lower than that of pure LiBH4, and reaches a hydrogen desorption capacity of 13.6% at 400 °C. When rehydrogenated under the condition of 6 MPa H2 and 350 °C, it has a reversible hydrogen storage capacity of 6%, while pure LiBH4 shows almost no reversible hydrogen storage capacity under the same condition. Mass spectrometry analysis（MS） results suggest that no diborane or other impurity gases are released in the decomposition process. The apparent activation energy of dehydrogenation of LiBH4 after confinement into AC decreases from 156.0 to 121.1 k J/mol, which leads to the eminent enhancement of dehydrogenation kinetics of LiBH4.

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 Ml0.80Mg0.20（Ni2.90Co0.50-Mn0.30Al0.30）x （x=0.68, 0.70, 0.72, 0.74, 0.76） alloys and Cu-substituted Ml0.80Mg0.20（Ni2.90Co0.50-yCuyMn0.30Al0.30）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. Ther-modynamic tests show that the enthalpy change in the dehydriding process decreases, indicating that hydride stability decreases with in-creasing 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 ame-liorates the discharge capacity, kinetics, and cycling stability of the alloy electrodes.

Electrochemical hydrogen storage properties of La_(0.95)Mg_(2.05)Ni_9 alloy prepared by mechanical alloying

The structure, microstructure, thermal stability and hydriding characteristics of amorphous La0.95-Mg2.05Ni9 have been investigated with differential thermal analysis, X-ray diffraction, scanning electron microscopy and battery test. It is found that the increase in mechanical alloying time leads to enhancement in thermal stabilities of amorphous La0.95Mg2.05Ni9 alloy. The amorphous alloy has good charge/discharge ability at room temperature(430 mA·h·g-1), but the discharge capacity decreases seriously during cycling tests due to the crystallization of amorphous and oxidization of magnesium on the particle surface in alkaline aqueous solution.

Li-Mg-N-H体系储氢材料的研究进展

在固态储氢材料中,Li-Mg-N-H体系储氢材料因其热力学性能好、可逆性好、理论储氢容量高等特点被认为是最有前景的储氢材料。然而,由于Li-Mg-N-H体系的动力学性能较差,导致其在200℃以上才能进行快速吸放氢反应。因此,文章从成分调控、纳米化和掺杂催化剂3个方面论述了Li-Mg-N-H体系热力学和动力学调控的研究现状,并指出未来研究方向。

Hydrogen sorption properties of nanocrystalline Mg_2FeH_6-based complex and catalytic effect of TiO_2

The diversities of hydrogen sorption properties of Mg2FeH6-based complexes with and without TiO2 were investigated. Mg2FeH6-based complexes with and without TiO2 were synthesized respectively by reactive mechanical alloying,and hydrogen sorption properties of the complexes were examined by Sieverts-type apparatus. The results show that the sample without TiO2 releases 4.43 % (mass fraction) hydrogen in 1.5 ks at 653 K under 0.1 MPa H2 pressure and absorbs 90% of the total 4.43 % (mass fraction) hydrogen absorbed in 85 s at 623 K under 4.0 MPa H2 pressure. But for the sample with TiO2 addition under the same condition,it only needs 400 s to release all of the stored hydrogen and 60 s to absorb 90% of the total hydrogen absorbed. The activation energies for desorption process of the samples with and without TiO2 are determined to be 71.2 and 80.3 kJ/(mol.K),respectively. The improvement in hydrogen sorption rate and and reduction in activation energy can be attributed to the addition of TiO2.

大型液氢储罐内罐材料研究与应用进展

国外液氢应用技术起步较早,液氢储罐的设计制造能力已达到最大3800 m^(3)储罐应用案例,相关技术主要由美、日、俄等国所掌握;中国液氢应用技术起步较晚,液氢储罐设计制造能力上限为300 m^(3)储罐,与国际先进水平相比还有较大差距。由于液氢储罐内罐材料的设计、制造属于其最关键核心技术之一,因此,该文综述了液氢储罐内罐材料的研究进展及发展现状,并对生产标准、中国制造能力等进行分析,对下一步液氢储罐材料的技术开发和试制提出建议。

Effect of Preparation Methods on Hydriding Properties of La1.5Mg17 Ni0.5 Composite Materials

La1.5Mg17Ni0.5 hydrogen storage materials were prepared by hydriding combustion synthesis (HCS) and mechanical alloying (MA) method respectively. The experimental results show that the hydrogen absorption properties of La1.5Mg17Nio.5 prepared by MA are better than that by HCS. La1.5Mg17Nio.5 prepared by MA can absorb 6.73 mass% hydrogen at 523 K within 1 min, and 4.92 mass% hydrogen at 423 K. The improvement of hydriding properties of La1.5Mg17Ni0.5alloy prepared by MA can be ascribed to the formation of nano-crystalline and defects during the mechanical alloying.

Influence of TiC catalyst on absorption/desorption behaviors and microstructures of sodium aluminum hydride

TiC-doped NaA1H4 complex hydrides were prepared by hydrogenation of ball-milled Nail/A1 mixture with x TiC powder （x = 0, 5%, 8%, 10%, mole fraction）. The effects of TiC catalyst content on the absorption/desorption behaviors of the samples were investigated. The results show that TiC can improve the hydriding/dehydriding kinetics of sodium aluminum hydride, the hydriding rate of the sample increases with increasing TiC content. It is found that the TiC-doped NaA1H4 composites have a relatively good cyclic stability. The composite doped with 10% TiC maintains steadily about 4.5% （mass fraction） hydrogen absorption capacity as against about 3.8% （mass fraction） hydrogen desorption capacity over 8 cycles. The particle sizes of the TiC-doped NaA1H4 composites can be reduced to 50-100 nm, which may play an important role in improving the hydriding/dehydriding kinetics.

稀土储氢材料的研究进展

稀土储氢材料具有易活化,吸放氢平台平坦、压力适中、压差小,抗杂质气体中毒性能好,适合室温操作等优点,作为镍氢二次电池(Ni/MH)电极材料被广泛应用,在氢燃料电池领域作为安全高效的储氢材料也发挥着越来越重要的作用。综述了目前面向应用的LaNi_(5)型和超晶格型稀土储氢材料近些年的主要研究进展,重点介绍了组分优化、结构控制和性能衰减机理方面的研究,最后讨论了稀土储氢材料应用面临的挑战和未来的发展方向。我国稀土资源丰富,大力拓展稀土储氢材料在氢能和二次电池产业的应用,对我国稀土资源的综合利用具有重大的战略意义。

Li-Al-B-H复合储氢材料的制备及储氢性能研究

硼氢化锂(LiBH_(4))的有效储氢密度可达13.6%(质量分数,下同),是一种具有潜在应用前景的储氢材料。但是,LiBH_(4)的热力学稳定性高,导致其吸放氢温度高,且其吸放氢动力学差,可逆条件苛刻,严重限制了其实际应用。针对这些问题,以普通Al粉(记为“Al”)和纳米Al粉(记为“nano-Al”)作为改性添加剂,采用机械球磨法制备了LiBH_(4)+0.5Al和LiBH_(4)+0.5nano-Al(物质的量之比)这2种Li-Al-B-H复合储氢材料,并通过X射线衍射(XRD)、吸放氢测试、热分析等手段研究了2种Al粉制备的Li-Al-B-H复合储氢材料的微结构和放氢性能。放氢性能研究表明,添加Al后,LiBH_(4)的放氢温度得到降低,且以纳米Al粉构建的Li-Al-B-H复合储氢材料具有比以普通Al粉构建的Li-Al-B-H复合储氢材料更优异的放氢性能和循环性能。放氢产物微结构研究表明,在放氢过程中,LiBH_(4)会与Al发生反应生成AlB_(2)和Li-Al-B相,这是LiBH_(4)吸放氢性能提高的关键。另外,由于纳米Al的颗粒尺寸小,比表面积大,反应界面更多,使得LiBH_(4)+0.5nano-Al放氢后生成的AlB_(2)和Li-Al-B相的量比LiBH_(4)+0.5Al更多,这是LiBH_(4)+0.5nano-Al放氢性能优于LiBH_(4)+0.5Al的原因。研究结果将为进一步理解Li-Al-B-H复合储氢材料的储氢性能和储氢机理提供参考。

固体储氢材料的研究进展

氢的廉价制取、安全储运以及高效应用是目前氢能研究领域的重点,而安全、高效的氢储运是实现氢能规模化应用的技术关键,因此高容量固态储氢材料的研发具有重要的学术意义和应用价值。固体材料储氢因储氢密度大、安全系数高而成为最有前景的储氢技术,得到了研究者们的广泛关注。本文针对目前国内外固体储氢材料研究现状,论述了几种固体储氢材料的研究进展,包括物理吸附类储氢材料、金属基储氢材料、配位氢化物和水合物储氢材料。重点评述了固态储氢材料中最具发展潜力的镁基储氢材料,并阐述了合金化、纳米化、添加催化剂以及复合轻金属配位氢化物等几种改性方法对镁基储氢材料储氢机理、微观结构、热力学性能、动力学性能的影响。制氢-储氢-用氢一体集成化设计应是固态储氢尤其是镁基储氢产业化应用发展道路,而镁基固态储运氢技术的发展,将可能实现氢气安全高效及大规模储运。

First-principles study of intrinsic defects,dopants and dopant-defect complexes in LiBH_4

A first-principles study was reported based on density functional theory of hydrogen vacancy,metal dopants,metal dopant-vacancy complex in LiBH4,a promising material for hydrogen storage.The formation of H vacancy and metal doping in LiBH4 is difficult,and their concentrations are low.The presence of one kind of defect is helpful to the formation of other kind of defect.Based on the analysis of electronic structure,the improvement of the dehydrogenating kinetics of LiBH4 by metal catalysts is due to the weaker bonding of B—H and the new metal-like system,which makes H atom diffuse easily;H vacancy accounts for a trace amount of BH3 release during the decomposing process of LiBH4;metal dopant weakens the strength of B—H bonds,which reduces the dehydriding temperature of LiBH4.The roles of metal and vacancy in the metal dopant-vacancy complex can be added in LiBH4 system.

Investigations on hydrogen storage properties of LaMg_(8.52)Ni_(2.23)M_(0.15) (M=Ni, Cu, Cr) alloys

LaMg8.52Ni2.23M0.15 （M=Ni, Cu, Cr） alloys were prepared by induction melting. X-ray diffraction showed that all the three alloys had a multiphase structure, consisting of La2Mg17, LaMg2Ni and Mg2Ni phases. Energy dispersive X-ray spectrometer results revealed that most of Cu and Cr distributed in MgzNi phase. La2Mg17 and LaMg2Ni phases decomposed into MgHz, Mg2NiH4 and LaH3 phases during the hydrogenation process. Hydriding/dehydriding measurements indicated that the reversible hydrogen storage capacities of Mg2Ni phase in LaMgs.52Ni2.23M0.15 （M=Cu, Cr） alloys increased to 1.05 wt.% and 0.97 wt.% from 0.79 wt.% of Mg2Ni phase in LaMgs.52Ni2.38 alloy at 523 K. Partial substitution of Cu and Cr for Ni decreased the onset dehydrogenation temperature of the alloy hydrides and the temperature lowered by 18.20 and 5.50 K, respectively. The improvement in the dehydrogenation property of the alloys was attributed to that Cu and Cr decreased the stability of Mg2NiH4 phase.