储氢材料第一性原理计算的研究进展

综述了第一性原理计算在储氢材料研究中取得的成果和最新的进展。 第一性原理计算在储氢材料研究中的应用主要有以下4个方面： 1）研究纳米结构的储氢性能; 2） 研究储氢材料中掺杂和缺陷的作用及对储氢性能的影响; 3）研究储氢机理; 4）确定氢化物的几何结构以及预测新型储氢材料。 同时展望了第一性原理计算在储氢领域中的应用前景。     

纳米储氢合金

作为一种新型的清洁能源,氢能在日益严峻的能源危机中越来越重要。纳米储氢合金因其优异的性能,被认为是下一代重要的储氢材料。本文介绍了储氢合金的原理、储氢合金的动力学和热力学以及各种储氢材料性能。基于储氢合金的最新研究进展,本文综述了提高纳米合金储氢性能的措施、纳米储氢合金的制备方法及其优缺点,进一步探讨了影响纳米合金储氢性能的因素,对储氢合金的进一步发展进行了展望。     

纳米限域的储氢材料

氢能作为洁净、理想的二次能源,已受到世界各国的广泛关注。然而,氢的储存技术仍然是制约氢能商业化应用的关键技术。利用储氢材料进行储氢被认为是一种安全、高效的固态储氢方式。因此,开发新型高容量的储氢材料与储氢技术成为氢能领域研究的热点之一。纳米限域是将材料填充到纳米孔道里,利用材料和纳米孔道的相互作用促进反应的进行,为化学反应提供一个独特的微环境。近年来,纳米限域逐渐发展成为改善储氢材料热力学和动力学的新方法。本文综述了纳米限域的储氢材料的研究进展,从纳米限域的储氢材料制备、储氢性能、反应机理和存在的问题等方面进行讨论,并指出了纳米限域储氢材料的发展趋势。     

硼氢化锂储氢材料研究*

车载储氢是推进氢燃料车规模化商业应用的“瓶颈”环节,开发高性能车载储氢材料/技术成为当前能源及材料领域关注的热点。近年来,随着储氢材料领域的不断拓展,以硼氢化锂（LiBH₄）为典型代表的高储量配位金属氢化物日渐成为新兴的储氢材料研究热点。本文从体系成分/反应路径调整、纳米结构调制、阴/阳离子替代及催化体系构建等方面概述了改善LiBH4综合储/放氢性能的最新研究进展,旨在明确配位硼氢化物储氢材料研究中的关键问题及可能的解决途径。     

储氢材料Li_2Mg(NH)_2的结构和电子性质:第一原理研究

The structural and electronic properties of Li₂Mg(NH)₂ for hydrogen storage have been studied by first-principles calculation. The optimal unit cell parameters and the distance of N-H are determined, which are in good agreement with the experimental data. The bulk modules and the energies of zero pressure are obtained by using Murnaghan equation of states. The results show that the α-Li₂Mg(NH)₂ is a ground state configuration. The overlap population analysis shows that the N-Li/Mg ionic characteristics and N-H interaction of αphase are weaker than those of βphase. The valence band is dominated by the presence of N s and p states, hybridized with the H s state.     

储氢材料的研究与进展

本文详细介绍了氢作为一种洁净二次能源载体的优点及发展潜力，综合描述了金属储氢材料、矿物多孔储氢材料、有机液态储氢材料的储氢特性及最新研究状况。最后就储氢材料的发展提出自己的见解。     

稀土发光材料理论计算方法研究现状

稀土发光材料在激光、照明、显示、辐射探测等众多领域起着至关重要的作用,建立相应的微观理论对于稀土发光材料的进一步发展和应用有着重要的科学意义.然而,由于4f电子复杂的多组态特征和很强的相对论效应,使得对稀土发光性质的理论研究到目前为止主要集中在经验或半经验模型的层面上,不依赖于任何经验信息的第一性原理方法仍然面临很大的...     

储氢材料的研究与进展

本文详细介绍了氢作为一种洁净二次能源载体的优点及发展潜力,综合描述了金属储氢材料、矿物多孔储氢材料、有机液态储氢材料的储氢特性及最新研究状况.最后就储氢材料的发展提出自己的见解.     

纳米镁储氢材料吸放氢动力学性能的研究进展

综述近十年来国内外有关纳米镁储氢材料吸放氢动力学的研究现状和发展趋势.众多研究表明,应用高能球磨法制备纳米镁复合储氢材料,并以过渡金属氧化物为催化剂,或者用ABx型储氢合金与镁复合,都能显著改善镁的吸放氢动力学性能.     

锂离子电池正极材料的第一性原理

锂离子电池的发展主要依赖于电极材料的突破,解决现有电极材料存在的问题和预测新型未知材料是提高锂离子电池性能的关键,而第一性原理计算的出现能够较好地满足这一需求.本文介绍了第一性原理计算在锂离子电池正极材料研究方面的原理和应用,对该原理在正极材料的平均嵌锂电压计算、嵌/脱锂机理、结构稳定性研究及新材料预测等方面的应用进行了详细论述,并指出了这一理论计算工具在电池材料设计过程中的重要性和局限性.     

新型储氢材料及其热力学与动力学问题

氢能作为一种理想的二次能源受到了国内外科研工作者的广泛关注,研制可以在室温和较低压力下方便、安全、高效地储存氢能的材料是氢能发展的瓶颈.到目前为止,固态储氢材料以能量密度高及安全性好等优势被认为极具应用前景,其中以轻质元素构成的氢化物(包括硼氢化物/铝氢化物(可用通式A(MH4)n表示,其中A是碱金属(Li,Na,K)或碱土金属(Be,Mg,Ca);M是硼或铝;n=1～4)、氨基氢化物(如LiNH2等))、氨硼烷(NH3BH3)、金属有机骨架材料(MOFs)是新型储氢材料研究领域的热点,本文将着重就目前这几类储氢材料的研究当中所涉及到的一些热力学及动力学问题进行总结探讨.     

Computational design of multifunctional materials

We propose a general scheme for the computational design of new materials using density functional theory. We then apply the scheme to two classes of materials; ferromagnetic ferroelectrics and half-metallic antiferromagnets. Our first “designer” ferromagnetic ferroelectric has subsequently been synthesized and the predicted properties verified. Our computations on half-metallic antiferromagnets have stimulated experimental study but the phenomenon remains unconfirmed.     

Functionalized boranes for hydrogen storage

Using density functional theory, the generalized gradient approximation for the exchange‐correlation potential and Møller–Plesset perturbation theory we study the hydrogen uptake of Li‐ and Mg‐doped boranes. Specifically, we calculate the structures and binding energies of hydrogen molecules sequentially attached to LiB₆H₇, LiB₁₂H₁₃, Li₂B₆H₆, Li₂B₁₂H_12, MgB₆H₆, and MgB₁₂H₁₂. Up to three H₂ molecules can be bound quasi‐molecularly to each of the metal cations with binding energies per H₂ molecule ranging between 0.07 eV and 0.27 eV. The corresponding gravimetric densities lie in the range of 3.49 to 12 wt %, not counting the H atoms bound chemically to the B atoms.     

First-principle investigation of XSrH3 (X = K and Rb) perovskite-type hydrides for hydrogen storage

Hydrogen can be utilized as an energy source; therefore, hydrogen storage has received the most appealing examination interest in recent years. The investigations of hydrogen storage applications center fundamentally around the examination of hydrogen capacity abilities of recently presented compounds. XSrH₃ (X = K and Rb) compounds have been examined by density functional theory (DFT) calculations to uncover their different characteristics, as well as hydrogen capacity properties, for the first time. Studied compounds are optimized in the cubic phase, and optimized lattice constants are obtained as 4.77 and 4.99 Å for KSrH₃ and RbSrH₃, respectively. These hydrides have shown negative values of formation enthalpies as they are stable thermodynamically. XSrH₃ might be used in hydrogen storage applications because of high gravimetric hydrogen storage densities, which are 2.33 and 1.71 wt% for KSrH₃ and RbSrH₃, respectively. Moreover, electronic properties confirm the semiconductor nature of these compounds having indirect band gaps of values 1.41 and 1.23 eV for KSrH₃ and RbSrH₃, respectively. In addition, mechanical properties from elastic constants such as Young modulus and Pugh's ratio, also have been investigated, and these compounds were found to satisfy born stability conditions. Furthermore, Pugh's ratio and Cauchy pressure show that these hydrides have a brittle nature. Furthermore, thermodynamic properties such as entropy and Debye temperature have been examined using the quasiharmonic Debye model for different temperatures and pressures.     

Potassium silanide (KSiH3): a reversible hydrogen storage material

KSi silicide can absorb hydrogen to directly form the ternary KSiH₃ hydride. The full structure of α‐KSiD₃, which has been solved by using neutron powder diffraction (NPD), shows an unusually short Si? D lengths of 1.47 Å. Through a combination of density functional theory (DFT) calculations and experimental methods, the thermodynamic and structural properties of the KSi/α‐KSiH₃ system are determined. This system is able to store 4.3 wt % of hydrogen reversibly within a good P–T window; a 0.1 M Pa hydrogen equilibrium pressure can be obtained at around 414 K. The DFT calculations and the measurements of hydrogen equilibrium pressures at different temperatures give similar values for the dehydrogenation enthalpy (≈23 kJ mol^?1 H₂) and entropy (≈54 J K^?1 mol^?1 H₂). Owing to its relatively high hydrogen storage capacity and its good thermodynamic values, this KSi/α‐KSiH₃ system is a promising candidate for reversible hydrogen storage.     

Verification of DFT-predicted hydrogen storage capacity of VC3H3 complex using molecular dynamics simulations

Density functional theory (DFT) and Fourth‐order Möller–Plesset (MP4) perturbation theory calculations are performed to examine the possibility of hydrogen storage in V‐capped VC₃H₃ complex. Stability of bare and H₂ molecules adsorbed V‐capped VC₃H₃ complex is verified using DFT and MP4 method. Thermo‐chemistry calculations are carried out to estimate the Gibbs free corrected averaged H₂ adsorption energy which reveals whether H₂ adsorption on V‐capped VC₃H₃ complex is energetically favorable, at different temperatures. We use different exchange and correlation functionals employed in DFT to see their effect on H₂ adsorption energy. Molecular dynamic (MD) simulations are performed to confirm whether this complex adsorbs H₂ molecules at a finite temperature. We elucidate the correlation between H₂ adsorption energy obtained from density functional calculations and retaining number of H₂ molecules on VC₃H₃ complex during MDs simulations at various temperatures. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011     

Biomolecule-assisted synthesis and electrochemical hydrogen storage of porous spongelike Ni3S2 nanostructures grown directly on nickel foils

Nanothread-based porous spongelike Ni3S2 nanostructures were synthesized directly on Ni foil by using a simple biomolecule-assisted method. By varying the experimental parameters, other novel Ni3S2 nanostructures could also be fabricated on the nickel substrate. The electrochemical hydrogen-storage behavior of these novel porous Ni3S2 nanostructures was investigated as an example of the potential properties of such porous materials. The thread-based porous spongelike Ni3S2 could electrochemically charge and discharge with the high capacity of 380 mAh g(-1) (corresponding to 1.4 wt % hydrogen in single-walled nanotubes (SWNT)). A novel two-charging-plateaux phenomenon was observed in the synthesized porous spongelike Ni3S2 nanostructures, suggesting two independent steps in the charging process. We have demonstrated that the morphology of the synthesized Ni3S2 nanostructures had a noticeable influence on their electrochemical hydrogen-storage capacity. This is probably due to the size and density of the pores as well as the microcosmic morphology of different nickel sulfide nanostructures. These novel porous Ni3S2 nanostructures should find wide applications in hydrogen storage, high-energy batteries, luminescence, and catalytic fields. This facile, environmentally benign, and solution-phase biomolecule-assisted method can be potentially extended to the preparation of other metal sulfide nanostructures on metal substrates, such as Cu, Fe, Sn, and Pb foils.     

Phthalocyanine‐Based Organometallic Nanocages: Properties and Gas Storage

Phthalocyanine (Pc) molecules are well‐known flexible structural units for 1D nanotubes and 2D nanosheets. First‐principles calculations combined with grand canonical Monte Carlo simulations are used to obtain the geometries, electronic structures, optical properties, and hydrogen‐storage capacities of nanocages consisting of six Pc molecules with six Mg or Ca atoms. The primitive Pc cage has T_h symmetry with twofold degeneracy in the highest occupied molecular orbital (HOMO), and threefold degeneracy in the lowest unoccupied molecular orbital (LUMO); the corresponding HOMO–LUMO gap is found to be 0.97 eV. The MgPc and CaPc cages have O_h symmetry with a HOMO–LUMO gap of 1.24 and 1.13 eV, respectively. Optical absorption spectra suggest that the Pc‐based cages can absorb infrared light, which is different from the visible‐light absorption in Pc molecules. We further show that the excess uptake of hydrogen on MgPc and CaPc cages at 298 K and 100 bar (1 bar=0.1 MPa) is about 3.49 and 4.74 wt %, respectively. The present study provides new insight into Pc‐based nanostructures with potential applications.