Hydrogen storage in carbon nanostructures – still a long road from science to commerce?

Hydrogen storage in carbon nanostructures is still at a research level and not yet mature for industrial application. For the time being it is unfair to compare carbon nanostructures for hydrogen storage at the same level as metal hydrides or other established storage technologies, as not yet enough research has been carried out. Nevertheless we compare carbon nanostructures with well-established hydrogen-storage technologies to develop a feeling of the needs and to identify where bottlenecks might exist. We try to sketch the long route for carbon nanostructures to become a commercial product for hydrogen storage, with a focus on mobile applications. Received: 4 August 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

Hydrogen storage using carbon adsorbents: past, present and future

Interest in hydrogen as a fuel has grown dramatically since 1990, and many advances in hydrogen production and utilization technologies have been made. However, hydrogen storage technologies must be significantly advanced if a hydrogen based energy system, particularly in the transportation sector, is to be established. Hydrogen can be made available on-board vehicles in containers of compressed or liquefied H₂, in metal hydrides, via chemical storage or by gas-on-solid adsorption. Although each method possesses desirable characteristics, no approach satisfies all of the efficiency, size, weight, cost and safety requirements for transportation or utility use. Gas-on-solid adsorption is an inherently safe and potentially high energy density hydrogen storage method that could be extremely energy efficient. Consequently, the hydrogen storage properties of high surface area “activated” carbons have been extensively studied. However, activated carbons are ineffective in storing hydrogen because only a small fraction of the pores in the typically wide pore-size distribution are small enough to interact strongly with hydrogen molecules at room temperatures and moderate pressures. Recently, many new carbon nanostructured absorbents have been produced including graphite nanofibers and carbon multi-wall and single-wall nanotubes. The following review provides a brief history of the hydrogen adsorption studies on activated carbons and comments on the recent experimental and theoretical investigations of the hydrogen adsorption properties of the new nanostructured carbon materials. Received: 16 October 2000 / Accepted: 15 November 2000 / Published online: 9 February 2001     

Hydrogen storage in sonicated carbon materials

The hydrogen storage in purified single-wall carbon nanotubes (SWNTs), graphite and diamond powder was investigated at room temperature and ambient pressure. The samples were sonicated in 5 M HNO₃ for various periods of time using an ultrasonic probe of the alloy Ti-6Al-4V. The goal of this treatment was to open the carbon nanotubes. The maximum value of overall hydrogen storage was found to be 1.5 wt %, as determined by thermal desorption spectroscopy. The storage capacity increases with sonication time. The sonication treatment introduces particles of the Ti alloy into the samples, as shown by X-ray diffraction, transmission electron microscopy, and chemical analysis. All of the hydrogen uptake can be explained by the assumption that the hydrogen is only stored in the Ti-alloy particles. The presence of Ti-alloy particles does not allow the determination of whether a small amount of hydrogen possibly is stored in the SWNTs themselves, and the fraction of nanotubes opened by the sonication treatment is unknown. Received: 18 December 2000 / Accepted: 18 December 2000 / Published online: 9 February 2001     

二维Li+BC3结构高储氢容量的研究

本文基于第一性原理密度泛函理论, 证实了锂原子可以均匀地吸附在二维结构的BC₃片两侧, 同时被吸附的锂原子不会抱团. 通过计算表明, 被吸附的锂原子浓度达到33.3%时, Li+BC₃体系具有最高的储氢比例12.57 wt.%. 然后, 通过热力学分析预测了在室温 (300 K) 下, 115–250 atm之间, Li+BC₃体系可以达到上述储氢比例, 这不仅符合美国能源部的要求, 也满足了应用中的安全需要. 关键词： 第一性原理 储氢 3二维结构')" href="#">Li+BC₃二维结构     

Exclusive leptoproduction of \rho^0 mesons from hydrogen at intermediate virtual photon energies

Measurements of the cross section for exclusive virtual-photoproduction of mesons from hydrogen are reported. The data were collected by the HERMES experiment using 27.5 GeV positrons incident on a hydrogen gas target in the HERA storage ring. The invariant mass W of the photon-nucleon system ranges from 4.0 to 6.0 GeV, while the negative squared four-momentum of the virtual photon varies from 0.7 to 5.0 GeV. The present data together with most of the previous data in the intermediate W-domain are well described by a model that infers the W-dependence of the cross section from the dependence on the Bjorken scaling variable x of the unpolarized structure function for deep-inelastic scattering. In addition, a model calculation based on Off-Forward Parton Distributions gives a fairly good account of the longitudinal component of the production cross section for GeV. Received: 25 April 2000 / Revised version: 3 July 2000 / Published online: 25 September 2000     

电场中(MgO)2吸附H2的理论研究

电场诱导MgO材料吸附H2是一种有效的储氢方法,而较高的场强制约其广泛应用。本文在B3LYP/CC-PVTZ水平上对电场中 (MgO)2团簇的储氢性质进行了研究,结果表明仅需外加强度为0.005 a. u. 的电场,就能使其对单个H2在Mg/O上的吸附能由无电场时的-0.143/-0.091 eV提高到-0.202/-0.134 eV. 该场强远小于其他大尺寸MgO材料达到相同吸附强度所需的电场,表明降低材料尺寸是减少储氢所需电场强度的一种可能方法。计算还表明电场中(MgO)2最多能吸附8个H2,相应的质量密度达到16.7 wt%。     

三明治结构graphene-2Li-graphene的储氢性能

本文使用密度泛函理论中的广义梯度近似对扩展三明治结构graphene-2Li-graphene的几何结构、电子性质和储氢性能进行计算研究.计算得知:位于单层石墨烯中六元环面心位上方的单个Li原子与基底之间的结合能最大(1.19 eV),但小于固体Li的实验内聚能(1.63 eV),然而,在双层石墨烯之间的单个Li原子与基底的结合能增加到3.41 eV,远大于固体Li的实验内聚能,因此位于双层石墨烯之间的多个Li原子不会成簇,有利于进一步储氢.扩展三明治结构graphene-2Li-graphene中每个Li原子最多可以吸附3个H_2分子,储氢密度高达10.20 wt.%,超过美国能源部制定的5.5 wt.%的目标.该体系对1—3个H_2分子的平均吸附能分别为0.37,0.17和0.12 eV,介于物理吸附和化学吸附(0.1—0.8 eV)之间,因此该体系可以实现常温常压下对H_2的可逆吸附.通过对态密度分析可知,每个Li原子主要通过电场极化作用吸附多个H_2分子.动力学和巨配分函数计算表明graphene-2Li-graphene结构对H_2分子具有良好的可逆吸附性能.该研究可以为开发良好的储氢材料提供一个好的研究思路,为实验工作提供理论依据.     

电场中(MgO)2吸附H2的理论研究

电场诱导MgO材料吸附H2是一种有效的储氢方法,而较高的场强制约其广泛应用。本文在B3LYP/CC-PVTZ水平上对电场中 (MgO)2团簇的储氢性质进行了研究,结果表明仅需外加强度为0.005 a. u. 的电场,就能使其对单个H2在Mg/O上的吸附能由无电场时的-0.143/-0.091 eV提高到-0.202/-0.134 eV. 该场强远小于其他大尺寸MgO材料达到相同吸附强度所需的电场,表明降低材料尺寸是减少储氢所需电场强度的一种可能方法。计算还表明电场中(MgO)2最多能吸附8个H2,相应的质量密度达到16.7 wt%。     

电场中(MgO)_2吸附H_2的理论研究

电场诱导MgO材料吸附H_2是一种有效的储氢方法,而较高的场强制约其广泛应用.本文在B3LYP/CC-PVTZ水平上对电场中(MgO)_2团簇的储氢性质进行了研究,结果表明仅需外加强度为0.005a.u.的电场,就能使其对单个H_2在Mg/O上的吸附能由无电场时的-0.143/-0.091 eV提高到-0.202/-0.134 eV.该场强远小于其他大尺寸MgO材料达到相同吸附强度所需的电场,表明降低材料尺寸是减少储氢所需电场强度的一种可能方法 .计算还表明电场中(MgO)_2最多能吸附8个H_2,相应的质量密度达到16.7 wt%.     

Exploring the possibility of GaPNTs as new materials for hydrogen storage

The possibility of hydrogen storage in gallium phosphate nanotubes (GaPNTs) as a high-capacity hydrogen storage media is studied by employing ab-initio density functional theory (DFT) calculations with a van der Waals (VdW) correction. The binding energy, the distance of the adsorbed hydrogen molecules and the charge transfer were particularly calculated. The obtained results indicate that hydrogenation of the GaPNTs is sensitive to the curvatures and chiralities of the nanotubes. It is found that the binding energy of hydrogen physisorption on GaP nanotubes is higher that on carbon nanotubes. These results are useful in the search for a proper media for hydrogen storage at ambient conditions.     

Li原子修饰笼型Si_6团簇的结构和储氢性能

利用杂化密度泛函B3LYP方法,在6-311+G(d,p)基组水平上对Si_6和Li修饰的Si_6团簇的几何结构和电子性质及储氢性能进行模拟计算和理论研究.结果表明,Si_6团簇最低能量构型为笼型结构,纯Si_6团簇不能有效吸附氢分子.Li原子的引入显著改善了Si_6团簇的储氢能力.以两个Li原子端位修饰Si_6团簇为载体,其氢分子的平均吸附能为1.692~2.755 kcal/mol,每个Li原子周围可以有效吸附五个氢分子,储氢密度可达9.952 wt%.合适的吸附能和较高储氢密度表明Li修饰Si_6团簇有望成为理想的储氢材料.     

Li原子修饰笼型Si6团簇的结构和储氢性能

利用杂化密度泛函B3LYP方法, 在6-311+G(d, p)基组水平上对Si6和Li修饰的Si6团簇的几何结构和电子性质及储氢性能进行模拟计算和理论研究. 结果表明, Si6团簇最低能量构型为笼型结构, 纯Si6团簇不能有效吸附氢分子. Li原子的引入显著改善了Si6团簇的储氢能力. 以两个Li原子端位修饰Si6团簇为载体, 其氢分子的平均吸附能为1.692~2.755 kcal/mol, 每个Li原子周围可以有效吸附五个氢分子, 储氢密度可达9.952wt%. 合适的吸附能和较高储氢密度表明Li修饰Si6团簇有望成为理想的储氢材料.     

First-principles prediction of a ground state crystal structure of magnesium borohydride

Mg(BH(4))(2) contains a large amount of hydrogen by weight and by volume, but its promise as a candidate for hydrogen storage is dependent on the currently unknown thermodynamics of H2 release. Using first-principles density-functional theory calculations and a newly developed prototype electrostatic ground state search strategy, we predict a new T=0 K ground state of Mg(BH(4))(2) with I4[over ]m2 symmetry, which is 5 kJ/mol lower in energy than the recently proposed P6(1) structure. The calculated thermodynamics of H(2) release are within the range required for reversible storage.     

Mechanically alloyed metal hydride systems

Mechanosynthesis of metal hydrides is a new field in which important progress has been reported. In this paper, we present recent developments in mechanosynthesis of magnesium-based hydrides for storage applications. The effect of intense milling on magnesium and magnesium hydrides is presented. The influence of various additives on hydrogen-sorption properties is discussed with special emphasis on nanocomposite MgH₂+5 at. % V, where hydrogen-storage characteristics, cycling properties and the mechanism of hydrogen desorption are presented. The production of novel nanocrystalline porous structures by mechanical alloying followed by a leaching technique is discussed. Hot ball-milling, as a new method for rapid synthesis of alloys, is also presented. Finally, two other methods of production of metal hydrides are discussed. One is reactive milling where metal hydrides are synthesized by mechanical alloying under hydrogen pressure, while the other is milling elemental hydrides to produce complex hydrides. Received: 15 August 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

Combinatorial search for optimal hydrogen-storage nanomaterials based on polymers

We perform an extensive combinatorial search for optimal nanostructured hydrogen-storage materials among various metal-decorated polymers using first-principles density-functional calculations. We take into account the zero-point vibration as well as the pressure- and temperature-dependent adsorption-desorption probability of hydrogen molecules. An optimal material we identify is Ti-decorated cis-polyacetylene with reversibly usable gravimetric and volumetric density of 7.6 wt % and 63 kg/m(3), respectively, near ambient conditions. We also propose "thermodynamically usable hydrogen capacity" as a criterion for comparing different storage materials.     

Hydrogen storage in BC3 composite single-walled nanotube:a combined density functional theory and Monte Carlo investigation

This paper applies a density functional theory(DFT) and grand canonical Monte Carlo simulations(GCMC) to investigate the physisorptions of molecular hydrogen in single-walled BC 3 nanotubes and carbon nanotubes.The DFT calculations may provide useful information about the nature of hydrogen adsorption and physisorption energies in selected adsorption sites of these two nanotubes.Furthermore,the GCMC simulations can reproduce their storage capacity by calculating the weight percentage of the adsorbed molecular hydrogen under different conditions.The present results have shown that with both computational methods,the hydrogen storage capacity of BC 3 nanotubes is superior to that of carbon nanotubes.The reasons causing different behaviour of hydrogen storage in these two nanotubes are explained by using their contour plots of electron density and charge-density difference.     

Hydrogen storage in boron nitride and carbon clusters studied by molecular orbital calculations

Possibility of hydrogen gas storage in carbon (C) and boron nitride (BN) clusters was investigated by molecular orbital calculations. Chemisorption calculation was carried out for C₆₀, B₂₄N₂₄ and B₃₆N₃₆ with changing position of hydrogen atom to compare the bonding energy at carbon, nitrogen and boron, tetragonal and hexagonal rings. Chemisorption calculation of hydrogen for BN clusters showed that hydrogen bondings with nitrogen atoms and tetragonal rings were the most stable. Stability of H₂ molecules inside BN and C clusters was also investigated by molecular orbital calculations. C and BN clusters showed possibility of hydrogen storage of 6.5 and 4.9 wt%, respectively.     

Origin of the anomalous absence of hydride formation by ZrPd2

Intermetallic compounds based on hydrogen absorbing elements usually form stable hydrides. This is the case for PdZr2. Surprisingly, ZrPd2 does not absorb hydrogen although both compounds have the same crystal structure and satisfy the empirical geometrical criteria for hydride formation. Results of ab initio calculations reveal an unanticipated purely electronic origin. These results have implications in the search for new intermetallics for hydrogen storage.     

Nondissociative adsorption of H2 molecules in light-element-doped fullerenes

First-principles density functional and quantum Monte Carlo calculations of light-element doped fullerenes reveal significantly enhanced molecular H2 binding for substitutional B and Be. A nonclassical three-center binding mechanism between the dopant and H2 is identified, which is maximized when the empty p(z) orbital of the dopant is highly localized. The calculated binding energies of 0.2-0.6 eV/H2 is suited for reversible hydrogen storage at near standard conditions. The calculated H2 sorption process is barrier-less, which could also significantly simplify the kinetics for the storage.     

MgH2(110)表面Pd单原子催化氢脱附反应的第一性原理研究

本文采用第一性原理密度泛函理论计算研究了MgH₂(110)表面吸附单原子Pd后的氢脱附反应. 计算发现,在吸附一个Pd单原子后,MgH₂(110)表面氢脱附反应的能垒可以从1.802 eV显著地降低到1.154 eV,表明Pd单原子对于氢脱附具有很强的催化效应. 并且,Pd单原子催化还可以将氢脱附的温度从573 K显著地降低到了367 K,从而使MgH₂(110)表面的氢脱附反应更加容易和快速地发生. 此外,通过MgH₂(110)表面氢溢出机制的反向过程来讨论了氢脱附反应的微观过程. 该研究表明Pd/MgH₂薄膜在未来的实验中可作为良好的储氢材料.