基于物理吸附储氢材料的研究进展

doi:10.19799/j.cnki.2095-4239.2023.0029

摘要/Abstract

摘要：

氢能是可持续的二次清洁能源，在规模化应用的进程中，氢气的储运技术是制约氢能产业链发展的关键因素。物理吸附储氢技术是未来氢气安全应用的重要途径之一，但仍需克服储氢容量低和室温储氢难的技术难题。围绕物理吸附储氢技术研究，总结归纳了碳基材料(如活性炭、石墨烯、碳纳米管、介孔碳和碳气凝胶)、有机骨架材料[如金属有机骨架材料(MOFs)和共价有机骨架材料(COFs)]、水合物3类作为储氢材料的研发历程和研究进展，介绍了各类材料在提升储氢容量方面的研究成果和技术手段，同时分析了上述物理吸附储氢材料的储氢原理和在氢气储运利用上的技术特点，对比基于不同物理吸附机制的储氢材料优缺点，为氢储运技术应用提供进一步应用分析依据。最后针对未来固态储氢的发展趋势和目前的技术瓶颈，对物理吸附储氢技术突破点和发展方向提出建议。物理吸附储氢技术虽然具有明显的技术瓶颈，但与其他储氢技术结合形成复合储氢体系，仍然具有很好的协同效应，帮助提高储氢效率、改善吸放氢动力学和热力学性能，是储氢领域必要的技术分支。

关键词: 储氢, 物理吸附, 碳基材料, 有机骨架, 水合物

Abstract:

Hydrogen energy is a sustainable secondary clean energy. In large-scale applications, hydrogen storage and transportation technology are the key factors restricting the development of the hydrogen energy industry chain. Physical adsorption hydrogen storage technology is one of the important ways to safely apply hydrogen in the future. However, it still needs to overcome the technical problems of low hydrogen storage capacity and low absorption temperature. Focusing the research on physical adsorption hydrogen storage technology, the development history and research progress of carbon-based materials, such as activated carbon, graphene, carbon nanotubes, mesoporous carbon, and carbon aerogel, organic framework materials such as metal-organic framework materials (MOFs) and covalent organic framework materials (COFs), and hydrates such as hydrogen storage materials were summarized, and the research achievements and technical means of various materials in improving hydrogen storage capacity were introduced. Simultaneously, the hydrogen storage principle of the abovementioned physical adsorption hydrogen storage materials and their technical characteristics in hydrogen storage, transportation, and utilization were analyzed. The advantages and disadvantages of hydrogen storage materials based on different physical adsorption mechanisms were compared to provide a further application analysis basis for the application of hydrogen storage and transportation technology. Finally, the breakthrough and development direction of physical adsorption hydrogen storage technology were proposed according to the future development trend of solid hydrogen storage and the current technical limitations. Although the physical adsorption hydrogen storage technology has obvious technical limitations, it is still a necessary branch in the hydrogen storage field to combine with other hydrogen storage technologies to form a composite hydrogen storage system, which still has a good synergistic effect, helping to enhance the hydrogen storage efficiency and improve the dynamics and thermodynamic performance of hydrogen absorption and desorption processes.

Key words: hydrogen storage, physical adsorption, carbon-based materials, organic framework materials, hydrate

中图分类号:

TK 91

刘名瑞, 丁凯, 王唯, 孙进. 基于物理吸附储氢材料的研究进展[J]. 储能科学与技术, 2023, 12(6): 1804-1814.

Mingrui LIU, Kai DING, Wei WANG, Jin SUN. Research progress of hydrogen storage materials based on physical adsorption[J]. Energy Storage Science and Technology, 2023, 12(6): 1804-1814.

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样品	纯度	温度/K	压力/MPa	储氢量/%	参考文献
SWNT	热处理	77	0.1	1	Ansón等^[28]
SWNT	纯化	室温	4.8	1.2	Smith等^[29]
SWNT	非纯化	295	0.1	0.93	Nishimiya等^[30]
SWNT	非纯化	77	0.1	2.37	Nishimiya等^[30]
MWNT	非纯化	298	—	0.5	Ritschel等^[25]
MWNT	酸处理	300	1.0	13.8	Chen等^[31]
MWNT	高度纯化	300	7.0	0.7—0.8	Badzian等^[32]
CNT	酸处理	300	<7	0.5	García-García等^[33]
Co, Li loaded MWCNTs	纯化、活化	—	—	0.6—1.33	Aghababaei等^[34]
Ti-4ND-SWCNT	—		—	5.85	Ghosh等^[35]
Mg-5.7Zn-0.6Zr-CNT	—	280	—	7.13	Abbas等^[36]
SWNT-Ti-6Al-4V	纯化	室温	0.08	1.7	Hirscher等^[37]
SWNT-Fe	纯化	室温	0.08	<0.005	Hirscher等^[37]
Li-CNT	纯化	473～673	0.1	20	Chen等^[38]
K-CNT	纯化	<313	0.1	14	Chen等^[38]
Li-CNT (干H₂)	纯化	473~673	0.1	2.5	Yang^[39]
K-CNT (干H₂)	纯化	<313	0.1	1.8	Yang^[39]
MWNT-1 mol/L KNO₃	N₂气氛下热处理	室温	12	3.2	Huang^[40]

材料	特征	温度/K	压力/MPa	储氢量/%	参考文献
HKUST-1^①	473 K煅烧	303	3.5	0.47	Lin等^[71]
Zn_1.72Co_0.28(DHBDC)(DMF)_0.1^②	开放金属位	77	1	3.08	Botas等^[72]
Zn_0.78Co_1.22(DHBDC)(DMF)_0.1	开放金属位	77	1	2.73	Botas等^[72]
Co₂(DHBDC)(DMF)_0.09	开放金属位	77	1	3.23	Botas等^[72]
IRMOF-1^③		77	3.5	6.0	Mccarthy等^[73]
IRMOF-1		77	1.4	4.5	Tedds等^[74]
IRMOF-1		137	1.4	1.0	Tedds等^[74]
Cu₃(BTC)₂		77	1.4	4.2	Tedds等^[74]
Cu₃(BTC)₂		132	1.4	1.8	Tedds等^[74]
MNMOF-5^④		298	1.9	0.15	Xin等^[75]
Cu(II)-MOF	不饱和金属中心	77	6.2	6.6	Saha等^[76]
NJU-Bai12^⑤		77	2	5.24	Zheng等^[77]
MOF-808	(三氯甲基)碳酸酯上苯环存在缺电子态	77	4	7.31	Xu等^[78]
MOF-519^⑥		233	10	4.5	Rahali等^[79]
Cu-BTC		77	3	4.15	Chen等^[80]
COF-108-Li₆C₆₀		233	10	4.56	Ke等^[81]
COF-102		77	3.5	7.2	Furukawa等^[82]
COF-103		77	3.5	7.01	Furukawa等^[82]

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