镨、钕氢化物催化剂对NaH/Al复合物吸放氢性能的影响

采用NaH和Al为合成原料,镨、钕氢化物为催化剂,通过机械球磨(NaH/Al+6%(摩尔分数)RE-H)(RE=Pr,Nd)复合物的方法并加氢合成NaAlH4络合氢化物,系统研究了催化剂对其吸放氢性能的影响。结果表明,加入PrH2.92和NdH2.27能明显改善NaH/Al复合物的吸放氢动力学性能,有效降低NaAlH4的脱氢温度。(NaH/Al+6%PrH2.92)和(NaH/Al+6%NdH2.27)复合物的120℃吸氢容量分别为3.57%和3.61%(质量分数),170℃放氢容量分别为2.57%和2.95%;且两者均具有较好的吸放氢循环稳定性,但吸(放)氢后样品中均存在少量Na3AlH6相,表明样品的吸(放)氢反应进行得并不彻底,使得其实际吸放氢容量低于理论可逆储氢容量。研究表明,PrH2.92和NdH2.27在球磨、吸/放氢过程中始终稳态存在,起着催化储氢作用;(NaH/Al+6%PrH2.92)复合物的放氢活化能稍低于(NaH/Al+6%NdH2.27)复合物。     

Ti-Zr催化剂对NaH/Al复合物可逆储氢特性的影响

采用机械球磨(NaH/Al+Ti)和(NaH/Al+Ti-Zr)复合物的方法加氢制备了NaAlH4配位氢化物, 系统研究了Ti、Ti-Zr催化剂以及不同加氢条件对其可逆储氢行为的影响. 结果表明, 对于NaH/Al体系的吸放氢性能, 共掺金属Ti粉/Zr粉的催化作用比单独掺金属Ti粉的催化作用要好. 随着加氢温度从85 ℃上升到140 ℃, 体系的吸氢容量先增后减, 并在120 ℃时达到最大值; 同时, 发现共掺Ti-Zr催化剂的复合物具有最佳的储氢性能, 在120和85 ℃时的吸氢量分别为4.61%和3.52%(w), 比仅掺Ti 催化剂的复合物分别高出0.40%和0.70%(w)的吸氢量. 随着加氢压力的增大, (NaH/Al+Ti-Zr)复合物的吸氢性能随之提高. XRD和DSC分析结果表明, NaAlH4体系的放氢过程明显发生两步分解反应, 共掺Ti-Zr催化剂的复合物储氢性能优于单独掺Ti 催化剂的原因是, 共掺催化剂能有效改善NaAlH4体系吸放氢反应的动力学性能,并降低体系的放氢温度.     

络合氢化物Ti-NaAlH4的制备与储氢特性

采用Ti粉为催化剂前驱体、预处理Al粉和NaH为合成原料, 通过机械球磨-加氢方法合成出络合氢化物Ti-NaAlH4, 系统研究了球磨保护气氛、球磨时间和氢化加氢压力等制备参数对其储氢性能的影响. 结果表明, 制备方法对Ti-NaAlH4储氢特性有很大影响. 与氩气保护气氛相比, 在氢气气氛中球磨制备的复合物具有更高的吸放氢性能. 在氢气保护气氛下, 随着球磨时间从6 h增至24 h, 复合物的吸氢容量和吸氢速率先增后减, 12 h时达到最佳值, 而复合物的放氢容量和放氢速率则逐渐增高; 进一步延长球磨时间会使颗粒发生团聚, 从而导致吸氢性能下降. 随着氢化加氢压力从7.5 MPa升至13.5 MPa, 复合物的吸氢容量(质量分数)由2.83%逐渐增至4.21%. 复合物球磨后出现的Na3AlH6中间氢化物相表明, 在氢气下掺Ti球磨对NaH和Al的氢化反应起到很好的促进作用.     

Ti-Zr催化剂对NaH/A1复合物可逆储氢特性的影响

采用机械球磨(NaH/A1 Ti)和(NaH/A1 Ti-Zr)复合物的方法加氢制备了NaAIH4配位氢化物,系统研究了Ti、Ti-Zr催化剂以及不同加氢条件对其可逆储氢行为的影响.结果表明,对于NaH/A1体系的吸放氢性能,共掺金属Ti粉/Zr粉的催化作用比单独掺金属Ti粉的催化作用要好.随着加氢温度从85 ℃上升到140 ℃,体系的吸氢容量先增后减,并在120 ℃时达到最大值;同时,发现共掺Ti-Zr催化剂的复合物具有最佳的储氢性能,在120和85℃时的吸氢量分别为4.61％和3.52％(w),比仅掺Ti催化剂的复合物分别高出0.40％和0.70％(w)的吸氢量.随着加氢压力的增大,(NaH/A1 Ti-Zr)复合物的吸氢性能随之提高.XRD和DSC分析结果表明,NaA1H4体系的放氢过程明显发生两步分解反应,共掺Ti-Zr催化剂的复合物储氢性能优于单独掺Ti催化剂的原因是,共掺催化剂能有效改善NaA1H4体系吸放氢反应的动力学性能,并降低体系的放氢温度.     

KH添加对Na-Al-H配位氢化物可逆放氢性能的影响

以NaH粉和Al 粉为合成原料, 分别采用2% (摩尔分数, x) CeCl₃和2% CeCl₃/y% KH (y=0.02, 0.04)为催化添加剂, 在室温和3 MPa氢压下, 通过反应球磨(NaH/Al+CeCl₃)和(NaH/Al+CeCl₃/yKH) (y=0.02, 0.04)复合物成功制备出Na-Al-H 配位氢化物. 吸放氢性能测试结果表明, KH的加入能有效改善Na-Al-H 体系中第二步脱氢反应放氢动力学性能. (NaH/Al+CeCl₃/0.02KH)复合物170℃放氢时可在20 min内完成脱氢过程, 且在较低温度(100-140℃)下具有良好的可逆吸放氢性能. Kissenger 方法计算表明, 添加KH可降低Na-Al-H 体系第二步脱氢反应的表观活化能, 降低其放氢峰值温度. 相结构分析表明, KH的添加使Na-Al-H 体系中Na₃AlH₆的晶胞体积发生膨胀, 进而提高体系的第二步放氢动力学性能.     

Ti基准晶复相材料电极的电化学储氢性能

通过电弧熔炼和铜辊急冷技术分别制得Ti1.4V0.6Ni准晶材料和V5Ti9Zr26.2Ni38Cr3.5Co1.5Mn15.6Al0.4Sn0.8（VTZN）合金材料,再用球磨法得到Ti1.4V0.6Ni+20%(质量分数)VTZN的复相材料,研究了该复相材料的组织和电化学储氢特性。 结果表明,复相材料的相组成包括正二十面体准晶相（I-phase）、面心立方相（FCC）和体心立方相（BCC）。 复相材料作为镍氢电池负极,在303 K和放电电流密度为30 mA/g条件下,最大放电容量可达310 mA·h/g,放电性能优于Ti1.4V0.6Ni合金负极。     

球磨改性对(Ti Cr)_(0.497)V_(0.42)Fe_(0.083)/30%(w)(LaRMg)(NiCoAl)_(3.5)合金复合电极材料储氢和电化学性能的影响

以钒基合金(Ti Cr)0.497V0.42Fe0.083为基体,添加30%(w)稀土系A2B7型合金(LaRMg)(NiCoAl)3.5为电催化活性材料,采用机械球磨改性制备了储氢合金复合电极材料,研究其储氢特性和电化学性能.X射线衍射(XRD)、扫描电镜(SEM)和透射电子显微镜(TEM)分析结果表明,随球磨时间增加(t=0,0.5,1,3,5,10h),复合材料颗粒逐渐细化,A2B7型合金颗粒分散并包覆在钒基合金表面上;当球磨时间t≥5h时,复合材料形成明显的复合纳米晶组织并伴有部分非晶化倾向,同时钒基合金BCC相结构的晶胞参数a和晶胞体积V均明显减小.合金储氢特性及电化学性能分析测试结果表明,铸态纯钒基合金的吸氢量为3.11%(w),而球磨复合材料的储氢量随球磨时间增加呈减小的规律,其最大储氢量为2.47%(w);球磨改性后,复合材料电极的电催化性能得到明显改善,当球磨时间t≥3h时最大放电容量达到425.8mAh·g-1,经100次充放电循环后该电极的容量保持率(C100/Cmax)为97%,表现出良好的电极循环稳定性.     

铈添加对Ti16.5Cr20(V45Fe8.5)0.98Si2合金结构及储氢性能的影响

通过XRD,SEM,恒温等容储氢性能测试等方法,研究了Ce添加对Ti26.5Cr20(V45Fe8.5)0.98Si2Cex(x=0～2.0%(原子分数))合金结构及储氢性能的影响.结果表明,Ti16.5Cr20如(V45Fe8.5)0.98 Si2Cex(x=0～2.0%)合金为BCC和C14 Laves相双相合金,随合金中Ce添加量的增加,合金的晶格常数增大,而合金中C14 Laves相的含量减少.平衡压从0.233 MPa降低到0.167 MPa,合金的吸氢动力学性能得到改善,最大吸氢量也由3.08%增加至3.19%(质量分数),PCT曲线的平台斜率减小.合金的储氢性能的改善与Ce的加入抑制了部分C14 Laves相的析出,减少了合金中C14 Laves相的含量密切相关.     

钒基/稀土-镁-镍系A_2B_7型合金复合储氢材料的微观组织和电化学性能

以钒基合金(TiCr)0.497V0.42Fe0.083为基体,通过掺入稀土-镁-镍系A2B7型合金(MlMg)2(NiCoAl)7作为电催化活性物,采用机械球磨改性方法制备了储氢合金复合电极材料(TiCr)0.497V0.42Fe0.083+x(%,质量分数)(MlMg)2(NiCoAl)7(x=5～50),系统研究了电催化活性物含量对球磨复合材料微观组织和电化学性能的影响规律。XRD和SEM分析结果表明,随x值的增加,球磨后A2B7型合金颗粒细化后分散并包覆在钒基合金表面上;与铸态钒基合金相比,复合材料中BCC固溶体相结构的晶胞参数a和晶胞体积V均明显减小。电化学性能测试结果表明,球磨复合材料电极的最大放电容量随着x值的增加呈先增加后减小的变化规律,当x?5时,复合材料电极的放电容量为280～433.2mAh.g-1,其100次充放电循环后的电极容量保持率S100为92%～98.9%,表现出良好的电极循环稳定性,其中x=30时的复合材料的综合电化学性能较佳,A2B7型合金的抗腐蚀性能及其包覆效果以及V元素的溶出行为对球磨复合储氢合金电极的电化学循环稳定性具有重要的影响。随A2B7型合金含量x的增加,球磨复...     

影响TiMnx非计量比合金储氢容量的结构因素

以TiMn_x (x = 1.4, 1.5, 1.6, 1.7)非计量比合金为对象,系统研究了储氢容量与其内在结构之间的相关性。结果表明,所有合金的主相均为C14型Laves相,但其储氢容量却存在显著差异。其中TiMn_1.4合金的储氢量约为0.65% (w,质量分数),吸/放氢平台较倾斜,且存在明显的滞后;而TiMn_1.5合金的可逆储氢量达到1.2% (w),平台较为平坦;但继续增加x,其储氢量反而降低,如x = 1.6合金的储氢量仅为0.30% (w),而x = 1.7合金则几乎不吸氢。进一步结构解析表明,上述储氢容量的迥异主要归因于部分Ti原子占据Mn(2a)位置,且其占位率随x的增加而降低,随之C14相中贮氢四面体间隙体积减小;而引起贮氢四面体间隙体积发生变化的主要因素是Ti―Ti键和Mn(2a)―Mn(2a)键的键长,其中Mn(2a)―Mn(2a)键长的增加对合金储氢容量的提升起关键作用。     

TiCl3-enhanced NaAlH4: impact of excess al and development of the Al1-yTiy phase during cycling

NaAlH(4) with TiCl(3) and Al were mixed by ball-milling and cycled three times. The hydrogen storage properties were monitored during cycling, and the products were characterized by synchrotron X-ray diffraction. Because of the previously described formation of Al(1)(-)(y)Ti(y) with y approximately 0.15 during cycling that traps Al beyond the amount associated with the formation of NaCl, some Na(3)AlH(6) has no free Al to react with to form NaAlH(4). This was counteracted in the present work by adding a stoichiometric amount of Al that increases the theoretical storage capacity. Due to limitations in metal diffusion small amounts of Na(3)AlH(6) were still detected. When approximately 7 mol % more Al than the stoichiometric amount was added, the observed storage capacity increased significantly, and the Na(3)AlH(6) content was negligible after prolonged rehydrogenation. Cycled NaAlH(4) + 10 mol % TiCl(3) were desorbed to two different levels, and the diffraction patterns were compared. There is no change in unit-cell dimensions during desorption, and there is no sign of changes in the bulk composition of the Al(1)(-)(y)Ti(y) phase during a cycle. Adding pure Ti to a NaH + Al mixture by ball-milling in argon or hydrogen results in formation of TiH(2) that is stable during at least one cycle.     

钆对La-Mg-Ni系A_2B_7型储氢合金微观结构和电化学性能的影响

用高频感应熔炼方法制备了稀土系A2B7型La0.83-xGdxMg0.17N i3.05Co0.3A l0.15(x=0~0.5)储氢合金,在Ar气氛中和1173 K下对铸态合金进行退火处理,通过X射线衍射(XRD)、电子探针显微分析方法(EPMA)和电化学测试等分析方法系统研究了稀土Gd部分替代La元素对合金微观组织和电化学性能的影响规律。研究结果表明,合金退火组织主要由Ce2N i7型、Gd2Co7型、Pr5Co19型、PuN i3型和CaCu5型相组成,稀土Gd元素能有效减少和抑制退火组织中CaCu5型相的形成,随Gd含量x增加,合金相组成中A2B7型(Ce2N i7和Gd2Co7型)相丰度呈先增加后减小的规律,当x=0.2时其相丰度最大(91.0%)。合金的PCT吸氢平台压随Gd含量的增加而升高,x=0.5时吸氢平台压力接近0.1 MPa,x=0.2时合金的吸氢量达到最大值1.34%。电化学测试分析表明,随Gd含量x的增加,合金电极最大放电容量和容量保持率均呈先增加后减小的规律,适量的Gd元素可明显改善合金的综合电化学性能。当x=0.2时,合金电极放电容量达到最大值392.9 mAh.g-1,经100...     

Mg2 FeH6 纳米晶的制备及储氢性能

在室温和氩气气氛下, 以MgH2 和纳米Fe为原料, 采用机械合金化(球磨法)制备了Mg2FeH6纳米晶. 考察了球磨参数(时间、 转速)对产物的影响, 对所制备的Mg2FeH6 纳米晶的组成、 结构和形貌进行了表征, 并对其储氢性能进行了测试. 结果表明, 所制备的Mg2FeH6纳米晶为立方结构, 纯度较高(91.4%), 其晶粒尺寸较小, 约为10~30 nm, 但团聚现象较为严重. Mg2FeH6纳米晶具有较低的活化能和较好的吸放氢动力学性能, 其放氢的脱附焓和脱附熵分别为(-42.8±2) kJ/mol和(-72.0±3) J/(mol·K). 在503 K和6 kPa的氢气压力下, Mg2FeH6纳米晶在70 min内放氢量达到2.5%(质量分数); 在2 MPa的氢气压力下, 上述放氢产物具有较快的起始吸氢速率.     

Exploration of the nature of active Ti species in metallic Ti-doped NaAlH4

Clarification of the nature of active Ti species has been a key challenge in developing Ti-doped NaAlH(4) as a potential hydrogen storage medium. Previously, it has been greatly hindered by the invisibility of Ti-containing species in conventional analysis techniques. In the present study, for the first time, the catalytically active Ti-containing species have been definitely identified by X-ray diffraction in the hydrides doped with metallic Ti. It was found that mechanical milling of a NaH/Al mixture or NaAlH(4) with metallic Ti powder resulted in the formation of nanocrystalline Ti hydrides. The variation of the preparation conditions during the doping process leads to a slight composition variation of the Ti hydrides. The catalytic enhancement arising upon doping the hydride with commercial TiH(2) was quite similar to that achieved in the hydrides doped with metallic Ti. Moreover, the cycling stability that was previously established in metallic Ti-doped hydrides was also observed in the hydrides doped with TiH(2). These results clearly demonstrate that the in situ formed Ti hydrides act as active species to catalyze the reversible dehydrogenation of NaAlH(4). The mechanism by which Ti hydrides catalyze the reversible de-/hydrogenation reactions of NaAlH(4) was discussed.     

Understanding the role of Ti in reversible hydrogen storage as sodium alanate: a combined experimental and density functional theoretical approach

We report the results of an experimental and theoretical study of hydrogen storage in sodium alanate (NaAlH(4)). Reversible hydrogen storage in this material is dependent on the presence of 2-4% Ti dopant. Our combined study shows that the role of Ti may be linked entirely to Ti-containing active catalytic sites in the metallic Al phase present in the dehydrogenated NaAlH(4). The EXAFS data presented here show that dehydrogenated samples contain a highly disordered distribution of Ti-Al distances with no long-range order beyond the second coordination sphere. We have used density functional theory techniques to calculate the chemical potential of possible Ti arrangements on an Al(001) surface for Ti coverages ranging from 0.125 to 0.5 monolayer (ML) and have identified those that can chemisorb molecular hydrogen via spontaneous or only moderately activated pathways. The chemisorption process exhibits a characteristic nodal symmetry property for the low-barrier sites: the incipient doped surface-H(2) adduct's highest occupied molecular orbital (HOMO) incorporates the sigma antibonding molecular orbital of hydrogen, allowing the transfer of charge density from the surface to dissociate the molecular hydrogen. This work also proposes a plausible mechanism for the transport of an aluminum hydride species back into the NaH lattice that is supported by Car-Parrinello molecular dynamics (CPMD) simulations of the stability and mobility of aluminum clusters (alanes) on Al(001). As an experimental validation of the proposed role of titanium and the subsequent diffusion of alanes, we demonstrate experimentally that AlH(3) reacts with NaH to form NaAlH(4) without any requirement of a catalyst or hydrogen overpressure.