Ce2Mg17及其氢化物添加剂对LiBH4的放氢作用机理研究

为改善LiBH4体系的可逆吸放氢性能,将Ce2Mg17合金(简称为CM)及其氢化物(CeH2.51和MgH2,简称为CMH)分别与LiBH4球磨4 h制得LiBH4-0.02CM和LiBH4-0.02CMH复合储氢体系,采用MS、TPD、XRD和FT-IR等测试手段研究了不同状态Ce-Mg添加剂对复合储氢体系可逆吸放氢性能的影响及其作用机制。结果表明:Ce2Mg17合金本身对改善LiBH4吸放氢性能没有明显作用;而Ce2Mg17氢化物(即MgH2和CeH2.51)可降低复合体系中LiBH4的放氢温度和提高LiBH4的放氢速率,并可明显改善体系的可逆吸放氢性能。进一步分析表明,MgH2和CeH2.51对LiBH4的协同改性作用是有效降低LiBH4热力学稳定性、提高LiBH4-Ce-Mg复合体系可逆吸放氢性能的主要原因。     

Influence of lanthanon hydride catalysts on hydrogen storage properties of sodium alanates

NaAlH4 complex hydrides doped with lanthanon hydrides were prepared by hydrogenation of the ball-milled NaH/Al+ xmol.% RE-H composites (RE=La,Ce;x=2,4,6) using NaH and Al powder as raw materials. The influence of lanthanon hydride catalysts on the hydriding and dehydriding behaviors of the as-synthesized composites were investigated. It was found that the composite doped with 2 mol.% LaH3.01 displayed the highest hydrogen absorption capacity of 4.78 wt.% and desorption capacity of 4.66 wt.%, respectively. Moreover, the composite doped with 6 mol% CeH 2.51 showed the best hydriding/dehydriding reaction kinetics. The proposed catalytic mechanism for reversible hydrogen storage properties of the composite was attributed to the presence of active LaH3.01 and CeH2.51 particles, which were scattering on the surface of NaH and Al particles, acting as the catalytic active sites for hydrogen diffusion and playing an important catalytic role in the improved hydriding/dehydriding reaction.     

TiC催化剂对铝氢化钠吸放氢行为和微观结构的影响

采用氢化NaH/Al＋xTiC（x=0,5%,8%,10%,摩尔分数）混合物的方法制备TiC掺NaAlH4配位氢化物,系统研究TiC催化剂含量对样品吸放氢行为的影响。结果表明：TiC能有效改善铝氢化钠的吸放氢动力学性能,样品的加氢速率随着TiC含量的增加而提高;TiC掺NaAlH4复合物具有良好的吸放氢循环稳定性,掺杂10%TiC（摩尔分数）的NaAlH4复合物经过8次吸放氢循环后,其吸、放氢容量仍可稳定保持为4.5%和3.8%（质量分数）;TiC掺NaAlH4复合物的颗粒尺寸可降低到50-100nm,这对改善体系吸放氢反应动力学起到主要作用。     

(Ti-Cr)40V55Zr5储氢合金的热处理改性

研究了(Ti-Cr)10V55Zr5储氢合金在真空热处理(1473 K下保温2 h和6 h)改性前后的相结构及储氢性能.XRD及SEM分析表明,(Ti-Cr)40V55Zr5铸态合金由BCC结构的固溶体主相和ZrCr2基第二相组成;经过热处理后,合金的BCC主相的晶胞体积有所增大,除了BCC主相和ZrCr2基第二相外,还出现微量的富Ti第三相.储氢性能测试表明,热处理后(Ti-Cr)40V55Zr5合金的动力学性能和活化性能均得到改善,室温最大吸氢量略微降低,但P-C-T曲线放氢压力平台倾斜度降低,平台宽度稍有增大,80℃有效放氢量增大.研究表明,在1473 K下经2 h热处理改性的(Ti-Cr)40V55Zr5合金具有较好的综合性能,首次吸氢即可活化,室温吸氢量为401 ml·g-1,80℃有效放氢量达到240 ml·g-1.     

LiBH_4/Mg_(17)Al_(12)-氢化物复合体系的放氢行为改善及其机制(英文)

选择Mg17Al12-氢化物作为失稳剂与LiBH4进行球磨以改善LiBH4体系的吸放氢性能。研究表明,LiBH4/Mg17Al12-氢化物复合体系发生两步放氢过程。复合体系在300°C开始放氢并在500°C下产生9.8%的放氢量。通过添加Mg17Al12-氢化物,LiBH4的放氢动力学得到有效改善,并且其放氢温度降低20°C。复合体系的放氢产物在450°C的首次再加氢容量可高达8.3%。XRD分析表明,复合体系在放氢过程中所形成的MgB2和AlB2可降低LiBH4的热力学稳定性,进而有效改善LiBH4/Mg17Al12-氢化物复合体系的可逆储氢行为。