摘要
通过无压烧结法制备了固溶体MAX相(Ti_(0.5)V_(0.5))_3AlC_2,研究了其添加对MgH_2储氢性能的影响。结果发现,固溶体MAX相(Ti_(0.5)V_(0.5))_3AlC_2中的Ti和V元素通过协同作用,呈现出更高的催化活性。添加质量分数10%(Ti_(0.5)V_(0.5))_3AlC_2的MgH_2样品的起始放氢温度为230℃,较原始MgH_2降低了60℃。在275℃下等温放氢,(Ti_(0.5)V_(0.5))_3AlC_2添加样品的放氢速率可达0.35%·min~(-1),是原始MgH_2样品的4倍左右。此外,完全放氢后的MgH_2-10%(Ti_(0.5)V_(0.5))_3AlC_2样品在150℃、5 MPa氢压下,可在60 s内吸收4.7%的氢。计算显示,MgH_2-10%(Ti_(0.5)V_(0.5))_3AlC_2样品的表观活化能为79.6 kJ·mol~(-1),较原始MgH_2(153.8 kJ·mol~(-1))降低了48%,这是MgH_2放氢性能得到改善的主要原因。
A solid-solution MAX phase(Ti_(0.5)V_(0.5))_3AlC_2 was successfully synthesized with a pressureless sintering method, and its catalytic effect on hydrogen storage reaction of MgH_2 was systematically investigated. The solid solution MAX phase(Ti_(0.5)V_(0.5))_3AlC_2 exhibited superior catalytic activity, thanks to the synergistic catalysis effect of Ti and V. The on-set dehydrogenation temperature of MgH_2-10%(Ti_(0.5)V_(0.5))_3AlC_2 samples was only 230 ℃(mass fraction of(Ti_(0.5)V_(0.5))_3AlC_2 was 10%), which was 60 ℃ lower than that of pristine MgH_2. The desorption rate of MgH_2-10%(Ti_(0.5)V_(0.5))_3AlC_2 sample at 217 ℃ was calculated to be 0.35%·min~(-1), which was 4 times faster than that of the pristine sample. At 150 ℃, the dehydrogenated MgH_2-10%(Ti_(0.5)V_(0.5))_3AlC_2 sample absorbs 4.7% of H_2 within60 s under 5 MPa H_2. The apparent activation energy of the MgH_2-10%(Ti_(0.5)V_(0.5))_3AlC_2 sample was determined to be 79.6 kJ·mol~(-1), representing a 48% reduction in the reaction barrier, compared with pristine MgH_2(153.8 kJ·mol~(-1)). This reasonably explains the significant improvement in dehydrogenation performance.
引文
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