镁基储氢材料研究进展

从气固反应的角度对近几年镁基储氢材料研究中的新技术和新方法进行了综述。主要包括球磨法、晶态及非晶态改性、烧结法和添加添加剂等方法。并简要对各种方法的工艺条件及所制备产物的吸放氢性能进行了讨论。     

Hydrogen Storage in Partially Exfoliated Magnesium Diboride Multilayers

Metal boride nanostructures have shown significant promise for hydrogen storage applications. However, the synthesis of nanoscale metal boride particles is challenging because of their high surface energy, strong inter- and intraplanar bonding, and difficult-to-control surface termination. Here, it is demonstrated that mechanochemical exfoliation of magnesium diboride in zirconia produces 3–4 nm ultrathin MgB₂ nanosheets (multilayers) in high yield. High-pressure hydrogenation of these multilayers at 70 MPa and 330 °C followed by dehydrogenation at 390 °C reveals a hydrogen capacity of 5.1 wt%, which is ≈50 times larger than the capacity of bulk MgB₂ under the same conditions. This enhancement is attributed to the creation of defective sites by ball-milling and incomplete Mg surface coverage in MgB₂ multilayers, which disrupts the stable boron–boron ring structure. The density functional theory calculations indicate that the balance of Mg on the MgB₂ nanosheet surface changes as the material hydrogenates, as it is energetically favorable to trade a small number of Mg vacancies in Mg(BH₄)₂ for greater Mg coverage on the MgB₂ surface. The exfoliation and creation of ultrathin layers is a promising new direction for 2D metal boride/borohydride research with the potential to achieve high-capacity reversible hydrogen storage at more moderate pressures and temperatures.     

镀覆处理对LaNiAl合金贮氢性能影响*

用化学镀法和酸性镀法在ＬａＮｉ４.７５Ａｌ０.２５材料颗粒表面镀覆铜膜，然后压制成块。处理后材料的放氢速率、导热性能、抗粉化效果有显著提高，其中酸性镀得到的颗粒与化学镀得到的颗粒在元素分布、成分、吸氢量、抗粉化效果等上有较大差别，因此压块的放氢动力学和抗粉化效果也不同。     

高容量储氢材料的研究进展

氢能是一种理想的二次能源.氢能开发和利用需要解决氢的制取、储存和利用3个问题,而氢的规模储运是现阶段氢能应用的瓶颈.氢的储存方法有高压气态储存、低温液态储存和固态储存等3种.固态储氢材料储氢是通过化学反应或物理吸附将氢气储存于固态材料中,其能量密度高且安全性好,被认为是最有发展前景的一种氖气储存方式.由轻元素构成的轻质高容量储氢材料,如硼氢化物、铝氢化物、氨摹氢化物等,理论储氢容量均达到5%(质量分数)以上,这为固态储氢材料与技术的突破带来了希望.新型储氢材料未来研究的重点将集中于高储氢容量、近室温操作、可控吸/放氢、长寿命的轻金属基氢化物材料与体系.     

金属及化合物添加法对MgH2储氢性能的改进研究

近年来,氢化镁(MgH2)因具有较高的理论储氢容量而成为较有潜力的储氢材料之一,但由于MgH2在吸放氢反应过程中较差的热力学和动力学问题,抑制了它的实用化进程,因此需要对其储氢性能进行改善。综述了目前所采用或正在研究的改善氢化镁储氢性能的方法,即金属及化合物添加法,具体包括元素取代法、添加过渡金属氧化物或氟化物法等,比较了各种方法改善氢化镁储氢性能的优缺点,并指出其相关发展趋势。     

储氢材料研究进展

氢能作为一种新型的能量密度高的绿色能源,正引起世界各国的重视。储存技术是氢能利用的关键。储氢材料是当今研究的重点课题之一,也是氢的储存和输送过程中的重要载体。本文综述了目前已采用或正在研究的储氢材料,如金属(合金)储氢、碳基储氢、有机液体储氢、络合物储氢、硼烷氨储氢等材料,比较了各种储氢材料的优缺点,并指出其发展趋势。     

Complex Hydrides for Energy Storage,Conversion, and Utilization

Functional materials are the key enabling factor in the development of clean energy technologies. Materials of particular interest, which are reviewed herein, are a class of hydrogenous compound having the general formula of M(XH_n)_m, where M is usually a metal cation and X can be Al, B, C, N, O, transition metal (TM), or a mixture of them, which sets up an iono‐covalent or covalent bonding with H. M(XH_n)_m is generally termed as a complex hydride by the hydrogen storage community. The rich chemistry between H and B/C/N/O/Al/TM allows complex hydrides of diverse composition and electronic configuration, and thus tunable physical and chemical properties, for applications in hydrogen storage, thermal energy storage, ion conduction in electrochemical devices, and catalysis in fuel processing. The recent progress is reviewed here and strategic approaches for the design and optimization of complex hydrides for the abovementioned applications are highlighted.     

A Unique Double‐Layered Carbon Nanobowl‐Confined Lithium Borohydride for Highly Reversible Hydrogen Storage

Poor reversibility and high desorption temperature restricts the practical use of lithium borohydride (LiBH₄) as an advanced hydrogen store. Herein, a LiBH₄ composite confined in unique double‐layered carbon nanobowls prepared by a facile melt infiltration process is demonstrated, thanks to powerful capillary effect under 100 bar of H₂ pressure. The gradual formation of double‐layered carbon nanobowls is witnessed by transmission electron microscopy (TEM) observation. Benefiting from the nanoconfinement effect and catalytic function of carbon, this composite releases hydrogen from 225 °C and peaks at 353 °C, with a hydrogen release amount up to 10.9 wt%. The peak temperature of dehydriding is lowered by 112 °C compared with bulk LiBH₄. More importantly, the composite readily desorbs and absorbs ≈8.5 wt% of H₂ at 300 °C and 100 bar H₂, showing a significant reversibility of hydrogen storage. Such a high reversible capacity has not ever been observed under the identical conditions. The usable volumetric energy density reaches as high as 82.4 g L^?1 with considerable dehydriding kinetics. The findings provide insights in the design and development of nanosized complex hydrides for on‐board applications.     

Interface Modulation of MoS2/Metal Oxide Heterostructures for Efficient Hydrogen Evolution Electrocatalysis

Developing efficient earth‐abundant MoS₂ based hydrogen evolution reaction (HER) electrocatalysts is important but challenging due to the sluggish kinetics in alkaline media. Herein, a strategy to fabricate a high‐performance MoS₂ based HER electrocatalyst by modulating interface electronic structure via metal oxides is developed. All the heterostructure catalysts present significant improvement of HER electrocatalytic activities, demonstrating a positive role of metal oxides decoration in promoting the rate‐limited water dissociation step for the HER mechanism in alkaline media. The as‐obtained MoS₂/Ni₂O₃H catalyst exhibits a low overpotential of 84 mV at 10 mA cm^?2 and small charge‐transfer resistance of 1.5 Ω in 1 m KOH solution. The current density (217 mA cm^?2) at the overpotential of 200 mV is about 2 and 24 times higher than that of commercial Pt/C and bare MoS₂, respectively. Additionally, these MoS₂/metal oxides heterostructure catalysts show outstanding long‐term stability under a harsh chronopotentiometry test. Theoretical calculations reveal the varied sensitivity of 3d‐band in different transition oxides, in which Ni‐3d of Ni₂O₃H is evidently activated to achieve fast electron transfer for HER as the electron‐depletion center. Both electronic properties and energetic reaction trends confirm the high electroactivity of MoS₂/Ni₂O₃H in the adsorption and dissociation of H₂O for highly efficient HER in alkaline media.     

Nanopore-Supported Metal Nanocatalysts for Efficient Hydrogen Generation from Liquid-Phase Chemical Hydrogen Storage Materials

Hydrogen has emerged as an environmentally attractive fuel and a promising energy carrier for future applications to meet the ever-increasing energy challenges. The safe and efficient storage and release of hydrogen remain a bottleneck for realizing the upcoming hydrogen economy. Hydrogen storage based on liquid-phase chemical hydrogen storage materials is one of the most promising hydrogen storage techniques, which offers considerable potential for large-scale practical applications for its excellent safety, great convenience, and high efficiency. Recently, nanopore-supported metal nanocatalysts have stood out remarkably in boosting the field of liquid-phase chemical hydrogen storage. Herein, the latest research progress in catalytic hydrogen production is summarized, from liquid-phase chemical hydrogen storage materials, such as formic acid, ammonia borane, hydrous hydrazine, and sodium borohydride, by using metal nanocatalysts confined within diverse nanoporous materials, such as metal–organic frameworks, porous carbons, zeolites, mesoporous silica, and porous organic polymers. The state-of-the-art synthetic strategies and advanced characterizations for these nanocatalysts, as well as their catalytic performances in hydrogen generation, are presented. The limitation of each hydrogen storage system and future challenges and opportunities on this subject are also discussed. References in related fields are provided, and more developments and applications to achieve hydrogen energy will be inspired.     

Metal Hydride Nanoparticles with Ultrahigh Structural Stability and Hydrogen Storage Activity Derived from Microencapsulated Nanoconfinement

Metal hydrides (MHs) have recently been designed for hydrogen sensors, switchable mirrors, rechargeable batteries, and other energy‐storage and conversion‐related applications. The demands of MHs, particular fast hydrogen absorption/desorption kinetics, have brought their sizes to nanoscale. However, the nanostructured MHs generally suffer from surface passivation and low aggregation‐resisting structural stability upon absorption/desorption. This study reports a novel strategy named microencapsulated nanoconfinement to realize local synthesis of nano‐MHs, which possess ultrahigh structural stability and superior desorption kinetics. Monodispersed Mg₂NiH₄ single crystal nanoparticles (NPs) are in situ encapsulated on the surface of graphene sheets (GS) through facile gas–solid reactions. This well‐defined MgO coating layer with a thickness of ≈3 nm efficiently separates the NPs from each other to prevent aggregation during hydrogen absorption/desorption cycles, leading to excellent thermal and mechanical stability. More interestingly, the MgO layer shows superior gas‐selective permeability to prevent further oxidation of Mg₂NiH₄ meanwhile accessible for hydrogen absorption/desorption. As a result, an extremely low activation energy (31.2 kJ mol^–1) for the dehydrogenation reaction is achieved. This study provides alternative insights into designing nanosized MHs with both excellent hydrogen storage activity and thermal/mechanical stability exempting surface modification by agents.     

轻质金属-铝氢化物贮氢材料的研究进展

介绍了几种轻质金属-铝氢化物贮氢材料的吸放氢机理和研究进展.轻质金属-铝氢化物贮氢密度高,但存在动力学性能差、放氢温度高、可逆反应程度低等缺点,目前主要通过掺杂催化剂、降低材料的颗粒尺寸等方法来创提高吸放氢的速率和效率.随着研究的深入,轻质金属-铝氢化物在贮氢方面将有广阔的发展前景.     

硼氢化物吸放氢性能的研究进展

吸放氢热/动力学差及可逆条件苛刻是限制硼氢化物MBH4(M=Li,Na)储氢材料广泛应用的最大"瓶颈"。从价键特征以及吸放氢后相变化两个本质原因出发,分析总结了近年来硼氢化物储能材料的研究进展,重点阐述了反应物失稳法及纳米结构调制对其吸放氢性能的改善,并根据目前面临的主要问题提出了可能的发展趋势。     

Improving the Hydrogen Reaction Kinetics of Complex Hydrides

Alanates, borohydrides, and amides are complex hydrides with high concentration hydrogen that have been actively investigated for materials‐based hydrogen storage on‐board polymer electrolyte membrane fuel cell (PEMFC) vehicle applications. The major challenge is to release hydrogen at fuel cell working temperature range at fast enough rate without simultaneous desorption of fuel cell poisoning impurities. We review recent progress in hydrogen reaction mechanism and schemes for complex hydride hydrogen storage.     

用于超高压化学热压缩的稀土储氢合金研究

具有融氢净化和氢压缩于一体等重要特性的金属氢化物化学热压缩器将成为未来加氢站的核心设备.本文简要介绍了金属氢化物化学热压缩器的工作原理及其特点,针对金属氢化物化学热压缩器对储氢合金的要求,研究开发了一种储氢性能优良、适合于作为化学氢压缩机用的稀土系储氢合金(Mm-Ml-Ca)(Ni-Al)5,测定了合金热力学和动力学性能.利用该合金设计制作了一台氢容量大于1000L、氢压大于40.0 MPa的压缩器样机,在20℃时氢压小于3.0 MPa可吸氢饱和,165℃放氢可得氢压大于40.0 MPa的超高压产品氢.原料氢纯度为98%时,产品氢纯度达到99.9999%.并且对压缩器的热效率进行了计算,其热效率达到21.9%.     

纳米金属有机框架材料的储氢性能研究

采用溶剂热法制备了纳米金属有机框架材料,通过粉末x射线衍射(PXRD)、高分辨透射电镜(HRTEM)、红外光谱(FT-IR)、热重分析(TG)、差示扫描量热法(DSC)和压力-组成-温度测试仪(PCI)等分析和表征手段,获得了该材料结构、形貌、热稳定性和吸附性能等信息.该材料对不同吸附质(如水0.19 g/g和苯0.41 g/g),表现出不同的吸附能力,并具有双亲功能.在77 K,1.5 MPa条件,其储氢量为3.2%(质量分数,下同),包含微孔内填充的高压氢气时为3.4%,包含中孔、微孔内填充的高压氢气时为3.9%.     

B和C对Li-N-H络合氢化物储氢性能的影响

利用机械合金化方法制备了Li-N-H络合氢化物,并研究B、C作为催化剂对其储氢性能的影响. 结果表明：LiNH₂、Li₂NH为Li-N-H络合氢化物的主要储氢相,随B的加入,储氢相的非晶化程度提高. 虽然B、C的添加均使储氢量下降,但n(B)∶n(C)=1∶2的混合添加提高了有效储氢量,同时也提高吸放氢动力学性能;B的添加可有效降低可逆吸放氢温度,适当增加球磨时间,有利于提高可逆吸放氢量.     

Recent Advances on Mixed Metal Sulfides for Advanced Sodium-Ion Batteries

Sodium-ion batteries (SIBs) have drawn enormous attention in the past few years from both academic and industrial battery communities in view of the fascinating advantages of rich abundance and low cost of sodium resources. Among various electrode materials, mixed metal sulfides (MMSs) stand out as promising negative electrode materials for SIBs considering their superior structural and compositional advantages, such as decent electrochemical reversibility, high electronic conductivity, and rich redox reactions. Here, a summary of some recent developments in the rational design and synthesis of various kinds of MMSs with tailorable architectures, structural/compositional complexity, controllable morphologies, and enhanced electrochemical properties is presented. The effect of structural engineering and compositional design of MMSs on the sodium storage properties is highlighted. It is anticipated that further innovative works on the material design of advanced electrodes for batteries can be inspired.     

高容量储氢材料的研究进展

高容量储氢材料在燃料电池和储热等方面有着良好的潜在应用.从高体积密度(kg/m3)和高储氢质量分数两个方面综述了高容量储氢材料的国内外研究近况.从材料组成、制备工艺、材料的组织结构以及催化剂应用等方面重点评述了Mg2FeH6、LiBH4、NaBH4、LiAlH4、NaAlH4等储氢材料的研究进展,指出高容量储氢材料今后中长期研究的重点是NaAlH4、Mg2 FeH6等络合氢化物以及催化剂.