五氧化二钒促进MgH2/Mg室温吸氢※

doi:10.6023/A21120561

化学学报 ›› 2022, Vol. 80 ›› Issue (3): 303-309.DOI: 10.6023/A21120561 上一篇下一篇

所属专题：中国科学院青年创新促进会合辑

研究论文

五氧化二钒促进MgH₂/Mg室温吸氢^※

戴敏^a^,^b, 雷钢铁^a^,^*(), 张钊^b, 李智^c^,^d, 曹湖军^b^,^*(), 陈萍^b

a 湘潭大学化学学院环境友好化学与应用教育部重点实验室湘潭 411100
b 中国科学院大连化学物理研究所大连 116023
c 山东能源集团有限公司济南 250014
d 西安交通大学材料科学与工程学院西安 710049

投稿日期:2021-12-14 发布日期:2022-02-07
通讯作者: 雷钢铁, 曹湖军
作者简介:
^※ 庆祝中国科学院青年创新促进会十年华诞.
基金资助:
山东省重点研发计划(2020CXGC010402); 国家自然科学基金(51801197); 中国科学院青年创新促进会(2019189); 辽宁省自然科学基金(2021-BS-010)

Room Temperature Hydrogen Absorption of V₂O₅ Catalyzed MgH₂/Mg^※

Min Dai^a^,^b, Gangtie Lei^a(), Zhao Zhang^b, Zhi Li^c^,^d, Hujun Cao^b(), Ping Chen^b

a Key Laboratory of Environmentally Friendly Chemistry and Applications of Ministry of Education, School of Chemistry, Xiangtan University, Xiangtan 411100
b Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023
c Shangdong Energy Group Co. Ltd., Jinan 250014
d School of Material Science and Engineering, Xi'an Jiaotong University, Xi'an 710049

Received:2021-12-14 Published:2022-02-07
Contact: Gangtie Lei, Hujun Cao
About author:
^※ Dedicated to the 10th anniversary of the Youth Innovation Promotion Association, CAS.
Supported by:
Key R&D Program of Shandong Province(2020CXGC010402); National Natural Science Foundation of China(51801197); Youth Innovation Promotion Association of Chinese Academy of Science(2019189); Natural Science Foundation of Liaoning Province(2021-BS-010)

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摘要/Abstract

MgH₂因其储氢量高、来源广及价格低廉等优点而备受关注, 但其热力学稳定(ΔH≥76 kJ/mol-H₂)以及低温吸/放氢动力学缓慢等问题限制了它在氢能领域的广泛应用. 研究发现, 过渡金属氧化物能够显著改善MgH₂的储氢动力学性能. 系统研究了过渡金属氧化物V₂O₅对MgH₂储氢性能的改善作用. 与纯MgH₂相比, 在MgH₂中添加质量分数为5%的V₂O₅可以显著改善MgH₂的吸/脱氢动力学性能. V₂O₅掺杂MgH₂的起始脱氢温度降至175 ℃, 比同等条件处理的纯MgH₂降低了89 ℃. 值得注意的是, V₂O₅掺杂的MgH₂脱氢后, 在室温和3 MPa的氢压下, 30和180 min内吸收H₂的质量分数分别为2.1%和3.8%. 同等氢压下, 当温度提高到300 ℃时, 该样品可在1 min内吸收H₂的质量分数高达6.7%. 同时催化掺杂样品还表现出良好的循环稳定性, 20次循环后仍能维持质量分数为6.0%以上的可逆储/放氢量. 此外, V₂O₅改善MgH₂储氢性能的反应机理也通过多种手段表征得以阐明.

关键词: 氢化镁, 五氧化二钒, 室温吸氢, 动力学性能, 循环稳定性

Magnesium hydride is a promising hydrogen storage material due to its high hydrogen storage capacity, low cost and abundance. The gravimetric and volumetric hydrogen capacities of MgH₂ are about 7.6% and 110 g/L, respectively. However, its sluggish de/re-hydrogenation rates and high operating temperatures ranging between 300~400 ℃ restrict it in practical applications. Catalyzing has been proved to be an effective method to improve its hydrogen storage performance. In this work, V₂O₅ has been chosen as a catalyst for improving the de/re-hydrogenation kinetics of MgH₂. Experimental results show that MgH₂ doping with V₂O₅ (w=5%) has the best hydrogen storage properties among the doping amounts (w) of 2.5% to 10%. Comparing with the pristine MgH₂, the addition of V₂O₅ (w=5%) significantly improves the ab/desorption behaviors of MgH₂. V₂O₅ (w=5%) doped MgH₂ starts releasing hydrogen from 175 ℃ which is 89 ℃ lower than the additive-free as-milled MgH₂. It should be noted that the dehydrogenated V₂O₅ (w=5%) doped MgH₂, is able to absorb 2.1% and 3.8% in the mass fraction of H₂ respectivity, within 30 and 180 min at room temperature and 3 MPa hydrogen pressure. Under the same hydrogen pressure, when the temperature is increased to 300 ℃, the mass fraction of H₂ absorbed by the sample is as high as 6.7% within 1 min. In addition, the catalyzed system shows a good reversibility, after 20 cycles, the hydrogen capacity maintains above 6.0%. Compared with the pure MgH₂, the dehydrogenation apparent activation energy of V₂O₅ catalyzed sample decreased from 108 to 56 kJ•mol^–1. X-Ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) have been employed to investigate its reaction mechanism. It shows that the formation of metallic vanadium and low-oxidation vanadium during ball milling and dehydrogenation process play important roles in improving the de/re-hydrogenation kinetics of MgH₂/Mg system.

Key words: magnesium hydride, vanadium pentoxide, room temperature H₂ absorption, kinetics, cycling stability

引用此文

戴敏, 雷钢铁, 张钊, 李智, 曹湖军, 陈萍. 五氧化二钒促进MgH₂/Mg室温吸氢^※[J]. 化学学报, 2022, 80(3): 303-309.

Min Dai, Gangtie Lei, Zhao Zhang, Zhi Li, Hujun Cao, Ping Chen. Room Temperature Hydrogen Absorption of V₂O₅ Catalyzed MgH₂/Mg^※[J]. Acta Chimica Sinica, 2022, 80(3): 303-309.

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图/表 11

图1. MgH2和V2O5 (w=2.5%, 5%, 10%)催化改性MgH2的程序升温脱氢-质谱曲线

Figure 1. Temperature programmed desorption-mass spectra curves (TPD-MS) of as-milled MgH2 and V2O5 (w=2.5%, 5%, 10%) catalyzed MgH2

图2. MgH2和V2O5 (w=2.5%, 5%, 10%)催化MgH2的体积法脱氢测试曲线(从30 ℃升温到400 ℃, 升温速率2 ℃/min)

Figure 2. Volumertic hydrogen release curves of the as-milled MgH2 and V2O5 (w=2.5%, 5%, 10%) catalyzed MgH2 (from 30 to 400 ℃ with a heating rate of 2 ℃/min)

图3. MgH2+V2O5 (w=5%)在3和5 MPa氢气压力下的室温吸收曲线

Figure 3. Room-temperature hydrogen absorption curves of MgH2+V2O5 (w=5%) at 3 and 5 MPa

图4. MgH2在(a) 250和(b) 300 ℃以及MgH2+V2O5 (w=5%)在(c) 250和(d) 300 ℃的等温脱氢曲线

Figure 4. Isothermal dehydrogenation curves of MgH2 at (a) 250 and (b) 300 ℃, and MgH2+V2O5 (w=5%) at (c) 250 and (d) 300 ℃

图5. MgH2在(a) 100、(b) 200和(c) 300 ℃以及MgH2+V2O5 (w=5%)在(d) 100、(e) 200和(f) 300 ℃的等温吸氢曲线

Figure 5. Isothermal hydrogenation curves of MgH2 at (a) 100, (b) 200 and (c) 300 ℃, and MgH2+V2O5 (w=5%) at (d) 100, (e) 200 and (f) 300 ℃

图6. MgH2+V2O5 (w=5%)在300 ℃下的吸放氢循环曲线(吸氢、放氢起始压力分别为约3 MPa和0.01 MPa)

Figure 6. Reversible hydrogen desorption (under 0.01 MPa) and sorption (3 MPa) of MgH2+V2O5 (w=5%) at 300 ℃

图7. (a) MgH2和(b) MgH2+V2O5 (w=5%)样品在2, 4, 6, 8 ℃/min加热速率下的TPD-MS曲线以及(c) MgH2和MgH2+V2O5 (w=5%)样品对应的脱氢活化能拟合图

Figure 7. TPD-MS curves of (a) as-milled MgH2 and (b) MgH2+V2O5 (w=5%) at heating rates of 2, 4, 6, and 8 ℃/min, and (c) Kissinger plot of as-milled MgH2 and MgH2+V2O5 (w=5%)

图8. MgH2+V2O5 (w=5%)在300、330和345 ℃下的PCI脱氢曲线[插图是MgH2+V2O5 (w=5%)的Van't Hoff拟合曲线]

Figure 8. PCI desorption curves of MgH2+V2O5 (w=5%) at 300, 330 and 345 ℃ [inset is the Van't Hoff plot]

图9. MgH2+V2O5 (w=5%)球磨、脱氢、第1次加氢和第20次加氢后的XRD图谱

Figure 9. XRD pattern of MgH2+V2O5 (w=5%) as-milled, dehydrogenated, the 1st hydrogenated and the 20th hydrogenated

图10. (a)原始MgH2, (b)球磨MgH2和(c)球磨MgH2+V2O5 (w=5%)的SEM图、MgH2+V2O5 (w=5%) (d)球磨后的EDS映射谱图、再氢化后的(e) TEM图和(f, g) HRTEM图

Figure 10. SEM images of (a) pristine MgH2, (b) as-milled MgH2 and (c) as-milled MgH2+V2O5 (w=5%), (d) EDS mapping of as-milled MgH2+V2O5 (w=5%), and (e) TEM image and (f, g) HRTEM images of hydrogenated MgH2+V2O5 (w=5%)

图11. (a) 纯V2O5、(b) MgH2+V2O5 (w=5%)脱氢和(c)再加氢样品的Ti 2p XPS谱图

Figure 11. Ti 2p XPS spectra of (a) pure V2O5, (b) dehydrogenated MgH2+V2O5 (w=5%) and (c) hydrogenated MgH2+V2O5 (w=5%)

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五氧化二钒促进MgH₂/Mg室温吸氢^※

Room Temperature Hydrogen Absorption of V₂O₅ Catalyzed MgH₂/Mg^※

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