氢能作为一种清洁、高效的能源形式,是解决全球变暖和能源危机的关键之一。然而由于氢气的重量轻、原子半径小、稳定性差,其高密度储存是影响发展和应用的瓶颈问题。氢化镁(MgH2)具有高储氢容量(7.6wt%、110kg H2/m3)、低成本和高安全性,被认为是极具潜力的固态储氢材料之一,但是其缓慢的动力学和高热力学稳定性难以满足实际应用的要求。纳米化改性可以提高MgH2的比表面积和晶界密度,同步改善其吸/放氢动力学与热力学性能。目前通过纳米化改性提升MgH2的储氢性能,已经取得了一系列研究成果。以纳米MgH2的制备方法、储氢性能和改性机理为重点对其进行归纳,并对纳米化MgH2储氢材料的发展和挑战进行了总结与展望。
Hydrogen energy,as a clean and efficient form of energy,is one of the key points to address global warming and the energy crisis.However,the high-density storage of hydrogen is a bottleneck restricting its development and application due to the light weight,small atomic radius and poor stability of hydrogen.Magnesium hydride (MgH2) is considered as one of the most promising solid-state hydrogen storage materials due to its high hydrogen storage capacity (7.6wt.%,110kg H2/m3),low cost,and high safety.While its slow kinetics and high thermodynamic stability hinder its practical application.Nanomodification can increase the specific surface area and grain boundary density of MgH2,thereby improving the hydrogen absorption/desorption kinetics and thermodynamic properties.Significant progress has been made in enhancing the hydrogen storage performance of MgH2 through nanomodification.In this paper,the preparation methods,hydrogen storage performance and modification mechanisms of nanostructured MgH2 were summarized,and provided an outlook on the future development and challenges of nanostructured MgH2 hydrogen storage materials.
[1] Tang D,Tan G L,Li G W,et al.State-of-the-art hydrogen generation techniques and storage methods:a critical review[J].Journal of Energy Storage,2023,64:107196.
[2] 邬娇娇,徐向亚,刘东兵,等.金属有机骨架材料在储氢领域的应用[J].化工新型材料,2023,51(11):16-21.
[3] Niaz S,Manzoor T,Pandith A H.Hydrogen storage:materials,methods and perspectives[J].Renewable and Sustainable Energy Reviews,2015,50:457-469.
[4] Usman M R.Hydrogen storage methods:review and current status[J].Renewable and Sustainable Energy Reviews,2022,167:112743.
[5] Abe J O,Popoola A P I,Ajenifuja E,et al.Hydrogen energy,economy and storage:review and recommendation[J].International Journal of Hydrogen Energy,2019,44(29):15072-15086.
[6] Song M C,Zhang L T,Wu F Y,et al.Recent advances of magnesium hydride as an energy storage material[J].Journal of Materials Science & Technology,2023,149:99-111.
[7] Yang X L,Lu X H,Zhang J Q,et al.Progress in improving hydrogen storage properties of Mg-based materials[J].Materials Today Advances,2023,19:100387.
[8] Bohmhammel K,Wolf U,Wolf G,et al.Thermodynamic optimization of the system magnesium-hydrogen[J].Thermochimica Acta,1999,337(1):195-199.
[9] Huang L,Peng L J,Li J,et al.Properties and microstructure of copper-titanium alloys with magnesium additions[J].Rare Metals,2024,43(5):2290-2299.
[10] Lin H J,Lu Y S,Zhang L T,et al.Recent advances in metastable alloys for hydrogen storage:a review[J].Rare Metals,2022,41(6):1797-1817.
[11] Sun Y H,Aguey-Zinsou K F.Dual-tuning the thermodynamics and kinetics:magnesium-naphthalocyanine nanocomposite for low temperature hydrogen cycling[J].International Journal of Hydrogen Energy,2018,43(10):5089-5097.
[12] Sun Y H,Ma T Y,Aguey-Zinsou K F.Magnesium supported on nickel nanobelts for hydrogen storage:coupling nanosizing and catalysis[J].ACS Applied Nano Materials,2018,1(3):1272-1279.
[13] Yan C,Lu X,Zheng J,et al.Dual-cation K2TaF7 catalyst improves high-capacity hydrogen storage behavior of MgH2[J].International Journal of Hydrogen Energy,2023,48(15):6023-6033.
[14] Li Z Y,Sun L X,Xu F,et al.Modulated noble metal/2D MOF heterostructures for improved hydrogen storage of MgH2[J].Rare Metals,2024,43:1672-1685.
[15] Ma Z L,Zang J H,Hu W Q,et al.From back to stage:superior cycling stability of 2LiBH4-MgH2 enabled by anion tuning[J].Advanced Energy Materials,2024,14(25):2401156.
[16] Wang X,Xiao X,Liang Z,et al.Ultrahigh reversible hydrogen capacity and synergetic mechanism of 2LiBH4-MgH2 system catalyzed by dual-metal fluoride[J].Chemical Engineering Journal,2022,433:134482.
[17] Yang H,Ding Z,Li Y T,et al.Recent advances in kinetic and thermodynamic regulation of magnesium hydride for hydrogen storage[J].Rare Metals,2023,42(9):2906-2927.
[18] Nielsen T K,Besenbacher F,Jensen T R.Nanoconfined hydrides for energy storage[J].Nanoscale,2011,3(5):2086-2098.
[19] Wagemans R W P,Van Lenthe J H,De Jongh P E,et al.Hydrogen storage in magnesium clusters:quantum chemical study[J].Journal of the American Chemical Society,2005,127(47):16675-16680.
[20] Schneemann A,White J L,Kang S,et al.Nanostructured metal hydrides for hydrogen storage[J].Chemical Reviews,2018,118(22):10775-10839.
[21] Huot J,Liang G,Boily S,et al.Structural study and hydrogen sorption kinetics of ball-milled magnesium hydride[J].Journal of Alloys and Compounds,1999,293:495-500.
[22] Varin R,Czujko T,Wronski Z.Particle size,grain size and γ-MgH2 effects on the desorption properties of nanocrystalline commercial magnesium hydride processed by controlled mechanical milling[J].Nanotechnology,2006,17(15):3856.
[23] Banrejee S,Kumar A,Ruz P,et al.Improvement of hydrogen storage characteristics of catalyst free magnesium nanoparticles prepared by wet milling[J].International Journal of Energy Research,2021,45(12):17597-17608.
[24] 施思婷.纳米MgH2的制备与储氢性能研究[D].广州:华南理工大学,2019.
[25] Berube V,Chen G,Dresselhaus M S.Impact of nanostructuring on the enthalpy of formation of metal hydrides[J].International Journal of Hydrogen Energy,2008,33(15):4122-4131.
[26] Huang L J,Shi S T,Cui J,et al.Thermally-assisted milling and hydrogenolysis for synthesizing ultrafine MgH2 with destabilized thermodynamics[J].Nanotechnology,2021,32(28):285402.
[27] Khan D,Zou J,Muhammad S,et al.The adaptable effect of Ru on hydrogen sorption characteristics of the MgH2 system[J].Materials Chemistry and Physics,2023,301:127583.
[28] Zhang X L,Liu Y F,Zhang X,et al.Empowering hydrogen storage performance of MgH2 by nanoengineering and nanocatalysis[J].Materials Today Nano,2020,9:100064.
[29] Tome K C,Xi S,Fu Y,et al.Remarkable catalytic effect of Ni and ZrO2 nanoparticles on the hydrogen sorption properties of MgH2[J].International Journal of Hydrogen Energy,2022,47(7):4716-4724.
[30] Berezovets V V,Denys R V,Zavaliy I Y,et al.Effect of Ti-based nanosized additives on the hydrogen storage properties of MgH2[J].International Journal of Hydrogen Energy,2022,47(11):7289-7298.
[31] De Jongh P E,Wagemans R W P,Eggenhuisen T M,et al.The preparation of carbon-supported magnesium nanoparticles using melt infiltration[J].Chemistry of Materials,2007,19(24):6052-6057.
[32] Gross A F,Ahn C C,Van Atta S L,et al.Fabrication and hydrogen sorption behaviour of nanoparticulate MgH2 incorporated in a porous carbon host[J].Nanotechnology,2009,20(20):204005.
[33] Han D J,Kwon C,Cho Y,et al.Tailoring hierarchical pore structures in carbon scaffolds for hydrogen storage of nanoconfined magnesium[J].Chemical Engineering Journal,2024,481:148451.
[34] Ren L,Li Y,Zhang N,et al.Nanostructuring of Mg-based hydrogen storage materials:recent advances for promoting key applications[J].Nano-Micro Letters,2023,15(1):93.
[35] Liu M,Zhao S,Xiao X,et al.Novel 1D carbon nanotubes uniformly wrapped nanoscale MgH2 for efficient hydrogen storage cycling performances with extreme high gravimetric and volumetric capacities[J].Nano Energy,2019,61:540-549.
[36] Ren L,Zhu W,Zhang Q,et al.MgH2 confinement in MOF-derived N-doped porous carbon nanofibers for enhanced hydrogen storage[J].Chemical Engineering Journal,2022,434:134701.
[37] Chen M,Xie X B,Liu P,et al.Facile fabrication of ultrathin carbon layer encapsulated air-stable Mg nanoparticles with enhanced hydrogen storage properties[J].Chemical Engineering Journal,2018,337:161-168.
[38] Xie X,Li Y,Chen M,et al.Catalytic effects of decorating AlV3 nanocatalyst on hydrogen storage performance of Mg@Mg17Al12 nanocomposite:experimental and theoretical study[J].ACS Sustainable Chemistry & Engineering,2020,8(12):4920-4930.
[39] Wang Y,Lan Z,Fu H,et al.Synergistic catalytic effects of ZIF-67 and transition metals (Ni,Cu,Pd,and Nb) on hydrogen storage properties of magnesium[J].International Journal of Hydrogen Energy,2020,45(24):13376-13386.
[40] Duan C W,Wu M M,Cao Y Z,et al.Novel core-shell structured MgH2/AlH3@CNT nanocomposites with extremely high dehydriding-rehydriding properties derived from nanoconfinement[J].Journal of Materials Chemistry A,2021,9(17):10921-10932.
[41] Li W,Li C,Ma H,et al.Magnesium nanowires:enhanced kinetics for hydrogen absorption and desorption[J].Journal of the American Chemical Society,2007,129(21):6710-6711.
[42] Sun Y H,Aguey-Zinsou K F.Synthesis of magnesium nanofibers by electroless reduction and their hydrogen interaction properties[J].Particle & Particle Systems Characterization,2017,34(4):1600276.
[43] Liu W,Aguey-Zinsou K F.Size effects and hydrogen storage properties of Mg nanoparticles synthesised by an electroless reduction method[J].Journal of Materials Chemistry A,2014,2(25):9718-9726.
[44] Aguey-Zinsou K-F,Ares-Fernández J-R.Synthesis of colloidal magnesium:a near room temperature store for hydrogen[J].Chemistry of Materials,2008,20(2):376-378.
[45] Setijadi E J,Boyer C,Aguey-Zinsou K F.Remarkable hydrogen storage properties for nanocrystalline MgH2 synthesised by the hydrogenolysis of Grignard reagents[J].Physical Chemistry Chemical Physics,2012,14(32):11386-11397.
[46] Setijadi E J,Boyer C,Aguey-Zinsou K F.MgH2 with different morphologies synthesized by thermal hydrogenolysis method for enhanced hydrogen sorption[J].International Journal of Hydrogen Energy,2013,38(14):5746-5757.
[47] Rambhujun N,Aguey-Zinsou K F.Halide-free Grignard reagents for the synthesis of superior MgH2 nanostructures[J].International Journal of Hydrogen Energy,2021,46(56):28675-28685.
[48] Zhang X,Liu Y F,Ren Z H,et al.Realizing 6.7wt% reversible storage of hydrogen at ambient temperature with non-confined ultrafine magnesium hydrides[J].Energy & EnvironmentaL Science,2021,14(4):2302-2313.
基金资助
国家自然科学基金(52201260);山东省自然科学基金(ZR2021QE071);科教产融合试点工程基础研究类项目(2023PY026);济南市“新高校20条”项目(202228073);山东省省属普通本科高校教师访学研修经费资助(2023年度)
PDF
