该文设计并制备了具有高储氢容量的BCC结构的 （Ti0.32Cr0.30V0.38）1-xFex （x=0、0.07、0.17） 合金,并采用原位氢化球磨法将其与Mg复合,研究不同Fe含量的 （Ti0.32Cr0.30V0.38）1-xFex合金对Mg基储氢材料的动/热力学性能的影响。采用Sievert’s体积法测试了合金及复合材料的储氢性能并使用XRD、SEM、TEM等对结构和形貌进行表征。结果表明,当x=0.07时,复合材料表现出最佳的储氢性能,起始放氢温度降低至219 ℃,在260 ℃下80 min内的放氢容量为4.22%（质量分数）,放氢焓变较相同制备方法得到的MgH2材料降低了13 kJ/mol。随着合金中Fe元素的增加,复合材料的放氢活化能逐渐降低,Mg/（Ti0.32Cr0.30V0.38）0.83Fe0.17的放氢活化能最低,为80.48 kJ/mol,主要原因在于原位生成的Mg2FeH6为放氢反应提供了活性位点,合金元素与Mg之间的电子转移使Mg的电子云密度降低,有利于H原子的解离。机理分析表明,（Ti0.32Cr0.30V0.38）0.93Fe0.07具有较高的硬度且在氢化球磨过程中抗粉化,更有利于Mg/（Ti0.32Cr0.30V0.38）0.93Fe0.07复合材料的晶粒细化和γ-MgH2的形成,使得复合材料的热力学性能提升。
Abstract
The （Ti0.32Cr0.30V0.38）1-xFex（x=0、0.07、0.17） alloys with a BCC structure and high hydrogen storage capacity were designed and prepared. These alloys with varying Fe contents were composited with Mg via reactive ball milling under a hydrogen atmosphere to study their effects on the kinetic and thermodynamic properties of the Mg-based hydrogen storage materials. The hydrogen storage properties of the alloys and composites were evaluated by Sieverts’volumetric method, while their microstructures were characterized by XRD, SEM, and TEM. The results demonstrate that the composite with x=0.07 exhibits optimal hydrogen storage performance, showing a reduced onset dehydrogenation temperature of 219 ℃ and a hydrogen desorption capacity of 4.22 wt% within 80 minutes at 260 ℃. Further, the dehydrogenation enthalpy is decreased by 13 kJ/mol compared to MgH2 prepared via the same synthesis method. The dehydrogenation activation energy of the composite exhibits a gradual reduction with increasing Fe content in the alloy. The Mg/（Ti0.32Cr0.30V0.38）0.83Fe0.17 composite exhibits the lowest dehydrogenation activation energy of 80.48 kJ/mol. The researche reveals that the in-situ formed Mg2FeH6 provides active sites for the dehydrogenation reaction, while the electron transfer between the alloy elements and Mg reduces the electron cloud density of Mg, thereby facilitating the dissociation of H atoms. The mechanism analysis reveals that （Ti0.32Cr0.30V0.38）0.93Fe0.07 exhibits high hardness and resists pulverization during reactive ball milling. These characteristics are more conducive to grain refinement and the formation of γ-MgH2 in the Mg/（Ti0.32Cr0.30V0.38）0.93Fe0.07 composite, ultimately enhancing its thermodynamic performance.
关键词
Mg /
储氢性能 /
BCC结构合金 /
γ-MgH2 /
原位氢化球磨
Key words
Mg /
hydrogen storage performance /
body-centered cubic alloys /
γ-MgH2 /
reactive ball milling
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基金
国家重点研发计划（2023YFB3809103）
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