轻质储氢材料的理论模拟研究进展

综述了近期有关轻质储氢材料(以轻元素为基础组成的储氢材料)的理论模拟进展情况,包括对于这类材料的晶体结构预测、掺杂改性机理研究以及复合储氢体系的化学反应过程研究等。指出轻质储氢材料代表了一大类已开发的和尚未开发的储氢体系,通过基于第一性原理的理论计算可以快速地筛选出具有合适热力学性质的高容量储氢反应;认为新近发展的晶体结构预测方法将在新型轻质储氢材料的理论设计上发挥重要作用。     

金属氰胺化合物的结构、合成及电化学储能应用

金属氰胺化合物M_x(NCN)_y作为类氧硫族化合物, 是一类新兴的无机功能材料。准线性[NCN]^2-阴离子赋予其空旷和具有孔道的晶体结构、独特的电子结构和新奇的物化性质, 金属氰胺化合物在固态发光、光/电催化及电化学储能等诸多领域展现出应用前景, 近年来逐渐成为研究热点。本文简要回顾了金属氰胺化合物的研究历史, 概述了金属氰胺化合物的晶体结构及物化性质, 总结了常见合成方法及策略, 探讨了金属氰胺化合物在电化学储能领域的应用, 重点论述了其作为锂钠离子电池新型负极材料的电化学性能及存储机制。     

Emerging characterization techniques for delving polyanion-type cathode materials of sodium-ion batteries

Polyanion-type cathode materials have grown in leaps and bounds and become one of the promising candidates for metal-ion batteries since the successful case of LiFePO₄ in lithium-ion batteries, which own stable crystal structure, high thermal stability, good ionic conductivity, adjustable voltage and chemical composition. However, further exploration is requisite, such as, the change of crystal/electronic structure, reaction mechanism, and structure evolution during charge/discharge processes, which results from variety of crystal types and redox centers, anion and cationic doping/substitution, as well as transition metal ion migration in polyanion-type materials. In this review, we focus on the advanced characterization techniques referred in polyanion-type cathode materials of sodium-ion batteries, mainly consist of the structure-related, morphology-related, composition-related techniques and in-situ/operando techniques during charge/discharge processes. The respective detection mechanisms, scope of application, information available and limitations of each technique are discussed in detail, and the latest developments of these characterization techniques used in polyanion-type materials are summarized. Advanced characterization techniques play a crucial role in understanding the reaction mechanisms of electrode materials, and can provide an important guiding principle for designing high-performance polyanion-type cathode materials and further optimizing the battery systems of sodium-ion batteries.     

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。     

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.     

Fabrication of Pd–DNA and Pd–CNT hybrid nanostructures for hydrogen sensors

This review reports fabrication methods for ordered metallic nanostructures such as nanowires and nanoparticles based on deoxyribonucleic acid (DNA) templates. The phosphate groups in DNA are negatively charged; consequently, the DNA conformation may mineralize metals, e.g., palladium (Pd) at a relatively high metal concentration. We successfully form unique spherically shaped moss-like hybrid Pd nanoparticles using the small compacted globular state of DNA by controlling the reductive reaction. Pd can absorb hydrogen to become PdH_x, and hydrogen storage increases the electrical resistance and volume of Pd materials. Hence, the use of this material is attracting growing interest as a reliable, cheap, ultracompact, and safe hydrogen sensor. Pd–DNA hybrid nanoparticles can be used as highly sensitive hydrogen sensors, which exhibit a switch response that depends on the volume expansion in a cyclic atmosphere exchange. This paper also shows the fabrications of Pd–carbon nanotube (CNT) hybrid nanostructures.     

Metal Organic Framework Derived Materials: Progress and Prospects for the Energy Conversion and Storage

Exploring new materials with high efficiency and durability is the major requirement in the field of sustainable energy conversion and storage systems. Numerous techniques have been developed in last three decades to enhance the efficiency of the catalyst systems, control over the composition, structure, surface area, pore size, and moreover morphology of the particles. In this respect, metal organic framework (MOF) derived catalysts are emerged as the finest materials with tunable properties and activities for the energy conversion and storage. Recently, several nano‐ or microstructures of metal oxides, chalcogenides, phosphides, nitrides, carbides, alloys, carbon materials, or their hybrids are explored for the electrochemical energy conversion like oxygen evolution, hydrogen evolution, oxygen reduction, or battery materials. Interest on the efficient energy storage system is also growing looking at the practical applications. Though, several reviews are available on the synthesis and application of MOF and MOF derived materials, their applications for the electrochemical energy conversion and storage is totally a new field of research and developed recently. This review focuses on the systematic design of the materials from MOF and control over their inherent properties to enhance the electrochemical performances.     

RE-oxide doped alkaline hydrogen storage materials prepared by mechanical activation

In the hydrogen energy system, hydrogen storage materials are considered to play an important role, such as H₂ storage and transportation media. In case of fuel-cell powered vehicles, storage material with large capacity and light weight are required. Alanates e.g., NaAlH₄, Na₃AlH₆ or Na₂LiAlH₆ have many advantages as hydrogen storage materials, because of their large hydrogen capacity, abundant in the earth crust and lower costs, etc. Alanates are, therefore, promising candidates for practical hydrogen transportation media, while investigations on their reaction kinetics with hydrogen are still insufficient. In this study, we prepared Na₂LiAlH₆ samples with different kinds of RE-oxides doped in the course of ball-milling. RE-oxides were used for improving hydrogen reactivity. Drastically improved hydrogen absorption kinetics obtained were discussed using thermodynamic consideration.     

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。     

纳米结构及离子束改性对储氢材料性能的影响

氢能作为一种高能量密度、清洁的绿色新能源,已受到人们的极大重视.传统的储氢材料存在吸放氢动力学差和释氢温度高的缺点,不利于使用.综述了纳米结构和离子束技术对储氢合金性能的影响,指出纳米化以及离子束改性是改善储氢合金动力学特性和释氢温度的有效途径.     

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: The major technological barrier to the development of hydrogen fuel cell cars

In this paper, we review the current technology for the storage of hydrogen on board a fuel cell-propelled vehicle. Having outlined the technical specifications necessary to match the performance of hydrocarbon. fue1, we first outline the inherent difficulties with gas pressure and liquid hydrogen storage. We then outline the history of transition metal hydride storage, leading to the development of metal hydride batteries. A viable system, however, must involve lighter elements and be vacuum-tight. The first new system to get serious consideration is titanium-activated sodium alanate, followed by the lithium amide and borohydride systems that potentially overcome several of the disadvantages of alanates. Borohydrides can alternatively produce hydrogen by reaction with water in the presence of a catalyst but the product would have to be recycled via a chemical plant. Finally various possible ways of making magnesium hydride decompose and reform more readily are discussed. The alternative to lighter hydrides is the development of physisorption of molecular hydrogen on high surface area materials such as carbons, metal oxide frameworks, zeolites. Here the problem is that the surface binding energy is too low to work at anything above liquid nitrogen temperature. Recent investigations of the interaction mechanism are discussed which show that systems with stronger interactions will inevitably require a surface interaction that increases the molecular hydrogen-hydrogen distance.     

Review of recent achievements in self-healing conductive materials and their applications

Self-healing materials have attracted increasing attention because of their wide range of applications. It can be expected to offer obvious advantages in conductive materials with self-healing properties, which are regarded as promising candidates for the fabrication of self-healing electronics, energy storage devices, sensors, anticorrosive coating and conductive adhesives. In this review, we focused on recent efforts to develop self-healing conductive composites including their preparation methods, properties and applications. The self-healing conductive materials were presented based on different conductive mediums, such as metal, carbon, conductive polymer, ionic liquids. In addition, their novel applications of the self-healing conductive materials in conductive coatings, energy storage devices and sensors are highlighted. Finally, the future challenges of conductive materials with self-healing properties are proposed.     

Materials for hydrogen storage

Hydrogen storage is a materials science challenge because, for all six storage methods currently being investigated, materials with either a strong interaction with hydrogen or without any reaction are needed. Besides conventional storage methods, i.e. high pressure gas cylinders and liquid hydrogen, the physisorption of hydrogen on materials with a high specific surface area, hydrogen intercalation in metals and complex hydrides, and storage of hydrogen based on metals and water are reviewed.The goal is to pack hydrogen as close as possible, i.e. to reach the highest volumetric density by using as little additional material as possible. Hydrogen storage implies the reduction of an enormous volume of hydrogen gas. At ambient temperature and atmospheric pressure, 1 kg of the gas has a volume of 11 m³. To increase hydrogen density, work must either be applied to compress the gas, the temperature decreased below the critical temperature, or the repulsion reduced by the interaction of hydrogen with another material.     

Emerging 2D Copper-Based Materials for Energy Storage and Conversion: A Review and Perspective

2D materials have shown great potential as electrode materials that determine the performance of a range of electrochemical energy technologies. Among these, 2D copper-based materials, such as Cu–O, Cu–S, Cu–Se, Cu–N, and Cu–P, have attracted tremendous research interest, because of the combination of remarkable properties, such as low cost, excellent chemical stability, facile fabrication, and significant electrochemical properties. Herein, the recent advances in the emerging 2D copper-based materials are summarized. A brief summary of the crystal structures and synthetic methods is started, and innovative strategies for improving electrochemical performances of 2D copper-based materials are described in detail through defect engineering, heterostructure construction, and surface functionalization. Furthermore, their state-of-the-art applications in electrochemical energy storage including supercapacitors (SCs), alkali (Li, Na, and K)-ion batteries, multivalent metal (Mg and Al)-ion batteries, and hybrid Mg/Li-ion batteries are described. In addition, the electrocatalysis applications of 2D copper-based materials in metal–air batteries, water-splitting, and CO₂ reduction reaction (CO₂RR) are also discussed. This review also discusses the charge storage mechanisms of 2D copper-based materials by various advanced characterization techniques. The review with a perspective of the current challenges and research outlook of such 2D copper-based materials for high-performance energy storage and conversion applications is concluded.     

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.     

金属有机骨架材料在光催化反应中的应用研究进展

环境问题和能源危机的是当今人类社会面临的两大重要问题。光催化技术被认为是解决环境问题和能源危机的有效途径之一。光催化技术利用的关键就是光催化材料的开发。金属有机骨架材料(Metal-organic frameworks,MOFs)是由金属或金属簇与有机配体构筑的一类具有周期性网络结构的新型多孔晶体材料,具有比表面积大、孔道结构规整、孔尺寸可调、催化活性位丰富等优点,被广泛应用于气体存储、气体分离、多相催化、半导体、仿生矿化等多个领域。近十几年来,众多科研工作者尝试将MOFs材料用于光催化反应,并取得了许多优秀的科研成果。尤其是近几年,MOFs在光催化领域的应用受到了越来越多科研工作者的关注。主要综述了近几年MOFs作为光催化剂在催化产氢、CO_2还原、烷基化反应、有机物氧化、有机还原、交叉脱氢偶联反应和去除环境污染物等方面的应用研究进展,并对未来MOFs光催化材料的发展提出了建议。     

Microscopic origin of the fast crystallization ability of Ge-Sb-Te phase-change memory materials

Ge-Sb-Te materials are used in optical DVDs and non-volatile electronic memories (phase-change random-access memory). In both, data storage is effected by fast, reversible phase changes between crystalline and amorphous states. Despite much experimental and theoretical effort to understand the phase-change mechanism, the detailed atomistic changes involved are still unknown. Here, we describe for the first time how the entire write/erase cycle for the Ge(2)Sb(2)Te(5) composition can be reproduced using ab initio molecular-dynamics simulations. Deep insight is gained into the phase-change process; very high densities of connected square rings, characteristic of the metastable rocksalt structure, form during melt cooling and are also quenched into the amorphous phase. Their presence strongly facilitates the homogeneous crystal nucleation of Ge(2)Sb(2)Te(5). As this simulation procedure is general, the microscopic insight provided on crystal nucleation should open up new ways to develop superior phase-change memory materials, for example, faster nucleation, different compositions, doping levels and so on.     

Molten salts for rechargeable batteries

The growing demand of advanced electrochemical energy storage devices for various applications, including portable electronic products, electric vehicles, and large-scale energy storage grids, has triggered extensive research interests and efforts on various rechargeable batteries such as lithium/sodium-ion batteries (LIBs/NIBs), aluminium-ion batteries (AIBs), liquid metal batteries (LMBs), and molten-air batteries (MABs) in the past decades. A key issue to push forward the development of these batteries is the exploration of high-performance electrodes and electrolytes, which calls for efficient and versatile synthetic methods. Molten salts (MSs), liquid-phase ionic compounds or mixtures, provide an effective platform to widen the reaction temperatures and enrich the chemical environments for the synthesis of novel electrode materials and electrolytes. In this review, the general principles of molten salts and recent research progresses on molten salt-based battery materials are surveyed. Molten-salt synthesis of electrode materials, including sintering and electrolysis, are emerging as competitive substitutes for conventional synthesis techniques. These methods have shown their effectiveness and uniqueness in adjusting the crystal structure, morphology, and performance of electrode materials for LIBs/NIBs, as suggested by recent progresses and applications of diverse cathodes (layered oxides, spinel oxides, polyanions, etc.) and anodes (metal oxides, alloys, carbons, etc.). Furthermore, the applications of molten salts as effective electrolytes are demonstrated in representative new-type secondary batteries including AIBs, LMBs and MABs. Finally, the emerging opportunities, challenges, and interesting research trends are envisioned to promote the further development of molten-salt methodology for rechargeable batteries.     

Supercritical hydrothermal synthesis of organic-inorganic hybrid nanoparticles

We have developed supercritical hydrothermal synthesis method of metal oxide nanoparticles where metal salt aqueous solution is mixed with high temperature water to rapidly increase the temperature of the metal salt solution and thus reduce the reactions and crystallizations during the heating up period. By using this method, we succeeded in the continuous and rapid production of metal oxide nanocrystals. A new method proposes to synthesize organic-inorganic fused materials based on the methods of supercritical hydrothermal synthesis. By introducing organic materials in a reaction atmosphere of supercritical hydrothermal synthesis, we successfully synthesized metal oxide nanoparticles whose surface was modified with organic materials. In supercritical state, water and organic materials form a homogeneous phase, which provides an excellent reaction atmosphere for the organic modification of nanoparticles. Modification with bio-materials including amino acids was also possible. By changing organic modifiers, particle morphology and crystal structure were changed. This organic surface modification provides a various unique characteristics for the nanoparticles: Dispersion of nanoparticles in aqueous solutions, organic solvents or in liquid polymers can be controlled by selecting hydrophilic or hydrophobic modifiers.