Nanostructured metal hydrides for hydrogen storage studied by in situ synchrotron and neutron diffraction

This work was focused on studies of the metal hydride materials having a potential in building hydrogen storage systems with high gravimetric and volumetric efficiencies of H storage and formed / decomposed with high rates of hydrogen exchange. In situ diffraction studies of the metal-hydrogen systems were explored as a valuable tool in probing both the mechanism of the phase-structural transformations and their kinetics. Two complementary techniques, namely Neutron Powder Diffraction (NPD) and Synchrotron X-ray diffraction (SR XRD) were utilised. High pressure in situ NPD studies were performed at D2 pressures reaching 1000 bar at the D1B diffractometer accommodated at Institute Laue Langevin, Grenoble. The data of the time resolved in situ SR XRD were collected at the Swiss Norwegian Beam Lines, ESRF, Grenoble in the pressure range up to 50 bar H2 at temperatures 20-400°C. The systems studied by NPD at high pressures included deuterated Al-modified Laves-type C15 ZrFe2-xAlx intermetallics with x = 0.02; 0.04 and 0.20 and the CeNi5-D2 system. D content, hysteresis of H uptake and release, unit cell expansion and stability of the hydrides systematically change with Al content. Deuteration exhibited a very fast kinetics; it resulted in increase of the unit cells volumes reaching 23.5 % for ZrFe1.98Al0.02D2.9(1) and associated with exclusive occupancy of the Zr2(Fe,Al)2 tetrahedra. For CeNi5 deuteration yielded a hexahydride CeNi5D6.2 (20°C, 776 bar D2) and was accompanied by a nearly isotropic volume expansion reaching 30.1% (∆a/a=10.0%; ∆c/c=7.5%). Deuterium atoms fill three different interstitial sites including Ce2Ni2, Ce2Ni3 and Ni4. Significant hysteresis was observed on the first absorption-desorption cycle. This hysteresis decreased on the absorption-desorption cycling. A different approach to the development of H storage systems is based on the hydrides of light elements, first of all the Mg-based ones. These systems were studied by SR XRD. Reactive ball milling in hydrogen (HRBM) allowed synthesis of the nanostructured Mg-based hydrides. The experimental parameters (PH2, T, energy of milling, ball / sample ratio and balls size), significantly influence rate of hydrogenation. The studies confirmed (a) a completeness of hydrogenation of Mg into MgH2; (b) indicated a partial transformation of the originally formed -MgH2 into a metastable -MgH2 (a ratio / was 3/1); (c) yielded the crystallite size for the main hydrogenation product, -MgH2, as close to 10 nm. Influence of the additives to Mg on the structure and hydrogen absorption/desorption properties and cycle behaviour of the composites was established and will be discussed in the paper.

Optimizing solar collector tilt angle to improve energy harvesting in a solar cooling system

Solar cooling systems are gaining popularity due to continuously increasing of energy costs around the world. However, there are still some factors that are hindering the installation of solar cooling systems on a larger scale. One being the cost associated with the solar collectors required to provide heat to the absorption chiller. This study demonstrates the possibility of reducing the number of solar panels in a residential solar cooling system based on evacuated tubes producing hot water at a low temperature (90 °C) and a water-ammonia absorption chiller.

Multifunctional three-dimensional T-junction graphene micro-wells: Energy-efficient, plasma-enabled growth and instant water-based transfer for flexible device applications

The “third-generation” 3D graphene structures, T-junction graphene micro-wells (T-GMWs) are produced on cheap polycrystalline Cu foils in a single-step, low-temperature (270 °C), energy-efficient, and environment-friendly dry plasma-enabled process. T-GMWs comprise vertical graphene (VG) petal-like sheets that seemlessly integrate with each other and the underlying horizontal graphene sheets by forming T-junctions. The microwells have the pico-to-femto-liter storage capacity and precipitate compartmentalized PBS crystals. The T-GMW films are transferred from the Cu substrates, without damage to the both, in de-ionized or tap water, at room temperature, and without commonly used sacrificial materials or hazardous chemicals. The Cu substrates are then re-used to produce similar-quality T-GMWs after a simple plasma conditioning. The isolated T-GMW films are transferred to diverse substrates and devices and show remarkable recovery of their electrical, optical, and hazardous NO2 gas sensing properties upon repeated bending (down to 1 mm radius) and release of flexible trasparent display plastic substrates. The plasma-enabled mechanism of T-GMW isolation in water is proposed and supported by the Cu plasma surface modification analysis. Our GMWs are suitable for various optoelectronic, sesning, energy, and biomedical applications while the growth approach is potentially scalable for future pilot-scale industrial production.

Ce1-xRuxO2-delta (x=0.05, 0.10): A New High Oxygen Storage Material and Pt, Pd-Free Three-Way Catalyst

Nanocrystalline Ce1-xRuxO2-delta (x = 0.05 and 0.10) of 8-10 nm sizes have been synthesized by hydrothermal method using melamine as complexing agent. Compounds have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray analysis (EDX) and their structures have been refined by the Rietveld method.The compounds crystallize in fluorite structure and the composition is Ce1-xRuxO2-x/2 where Ru is in +4 state and Ce is in mixed-valence (+3, +4) state. Substitution of Ru4+ ion in CeO2 activated the lattice oxygen. Ce1-xRuxO2-x/2 reversibly releases 0.22[O] and 0.42[O] for x = 0.05 and 0.10, respectively, which is higher than the maximumpossible OSC of 0.22 [O] observed for Ce0.50Zr0.50O2. Utilization of Higher OSC of Ce1-xRuxO2-delta (x = 0.05 and 0.10) is also reflected in terms of low-temperature CO oxidation with these catalysts, both in the presence and absence of feed oxygen. The Ru4+ ion acts as an active center for reducing molecules (CO, hydrocarbon ``HC'') and oxide ion vacancy acts as an active center for O-2 and NO, leading to low-temperature NO conversion to N-2. Thus due to Ru4+ ion, Ce1-xRuxO2-delta is not just a high oxygen storage material but also shows high activity toward CO, hydrocarbon ``HC'' oxidation, and NO reduction by CO at low temperature with high N-2 selectivity for three-way catalysis.

Urban energy fluxes in Helsinki and their high frequency spectral corrections

Inadvertent climate modification has led to an increase in urban temperatures compared to the surrounding rural area. The main reason for the temperature rise is the altered energy portioning of input net radiation to heat storage and sensible and latent heat fluxes in addition to the anthropogenic heat flux. The heat storage flux and anthropogenic heat flux have not yet been determined for Helsinki and they are not directly measurable. To the contrary, turbulent fluxes of sensible and latent heat in addition to net radiation can be measured, and the anthropogenic heat flux together with the heat storage flux can be solved as a residual. As a result, all inaccuracies in the determination of the energy balance components propagate to the residual term and special attention must be paid to the accurate determination of the components. One cause of error in the turbulent fluxes is the fluctuation attenuation at high frequencies which can be accounted for by high frequency spectral corrections. The aim of this study is twofold: to assess the relevance of high frequency corrections to water vapor fluxes and to assess the temporal variation of the energy fluxes. Turbulent fluxes of sensible and latent heat have been measured at SMEAR III station, Helsinki, since December 2005 using the eddy covariance technique. In addition, net radiation measurements have been ongoing since July 2007. The used calculation methods in this study consist of widely accepted eddy covariance data post processing methods in addition to Fourier and wavelet analysis. The high frequency spectral correction using the traditional transfer function method is highly dependent on relative humidity and has an 11% effect on the latent heat flux. This method is based on an assumption of spectral similarity which is shown not to be valid. A new correction method using wavelet analysis is thus initialized and it seems to account for the high frequency variation deficit. Anyhow, the resulting wavelet correction remains minimal in contrast to the traditional transfer function correction. The energy fluxes exhibit a behavior characteristic for urban environments: the energy input is channeled to sensible heat as latent heat flux is restricted by water availability. The monthly mean residual of the energy balance ranges from 30 Wm-2 in summer to -35 Wm-2 in winter meaning a heat storage to the ground during summer. Furthermore, the anthropogenic heat flux is approximated to be 50 Wm-2 during winter when residential heating is important.

A design approach to innovation in the Australian energy industry

Electricity businesses across Australia are facing many market disruptions, such as the increasing demand from the rapid uptake of domestic air conditioners and the contrasting problematic generation from solar power connections to the grid. In this context, the opportunity to proactively leverage forthcoming technological advances in battery storage and electric vehicles to address the steeply rising cost of electricity supply has emerged. This research explores a design approach to support a business to navigate such disruptions in the current market.This study examines a design-led approach to innovation conducted over a ten month action research study within a large, risk-averse firm in the Australian energy sector. This article presents results describing a current foresight gap within the business; the response of the business to using design-led innovation to address this issue; and the tools, approaches and processes used. The business responses indicate their perception of the value of qualitative customer engagement as a path to addressing, and potentially benefiting from, disruptive innovation. It is anticipated that these results will further business model development within the company, and assist in leveraging disruptive innovations for this industry participant, thus limiting future increases in the cost of electricity supply for customers in Australia.

Modelling conical rock-bed solar thermal storage tank

An important application of solar thermal storage is for power generation or process heating. Low-temperature thermal storage in a packed rock bed is considered the best option for thermal storage for solar drying applications. In this chapter, mathematical formulations for conical have been developed. The model equations are solved numerically for charging/discharging cycles utilizing MATLAB. Results were compared with rock-bed storage with standard straight tank. From the simulated results, the temperature distribution was found to be more uniform in the truncated conical rock-bed storage. Also, the pressure drop over a long period of time in the conical thermal storage was as low as 25 Pa. Hence, the amount of power required from a centrifugal fan would be significantly lower. The flow of air inside the tank is simulated in SolidWorks software. From flow simulation, 3D modelling of flow is obtained to capture the actual scenario inside the tank.

Mathematical modelling of rock-bed solar thermal storage tank

An important application of thermal storage is solar energy for power generation or process heating. Low temperature thermal storage in a packed rock bed is considered best option for thermal storage for solar drying applications. In this paper, mathematical formulations for conical and cylindrical rock bed storage tanks have been developed. The model equations are solved numerically for charging/discharging cycles. From the simulated results, it was observed that for the same aspect ratio between the diameter and the length of the thermal storages, the conical thermal storage had better performance. The temperature distribution was found to be more uniform in the truncated conical shape rock bed storage. Also, the pressure drop over long period of time in the conical thermal storage was lower than that of the cylindrical thermal storage. Hence, the amount of power required from a centrifugal fan was lower.

The application of islanded photovoltaic cells and battery storage on the reliability of distribution networks

Renewable energy resources, in particularly PV and battery storage are increasingly becoming part of residential and agriculture premises to manage their electricity consumption. This thesis addresses the tremendous technical, financial and planning challenges for utilities created by these increases, by offering techniques to examine the significance of various renewable resources in electricity network planning. The outcome of this research should assist utilities and customers for adequate planning that can be financially effective.

Performance evaluation of an integrated solar water heater as an option for building energy conservation

Since a majority of residential and industrial building hot water needs are around 50 degrees C, an integrated solar water heater could provide a bulk source that blends collection and storage into one unit. This paper describes the design, construction and performance test results of one such water-heating device. The test unit has an absorber area of 1.3 m(2) and can hold 1701 of water, of which extractable volume per day is 1001. Its performance was evaluated under various typical operating conditions. Every morning at about 7:00 a.m., 1001 of hot water were drawn from the sump and replaced with cold water from the mains. Although, during most of the days, the peak temperatures of water obtained are between 50 and 60 degrees C, the next morning temperatures were lower at 45-50 degrees C. Daytime collection efficiencies of about 60% and overall efficiencies of about 40% were obtained. Tests were conducted with and without stratification. Night radiation losses were reduced by use of a screen insulation.

Metallacarboranes: Toward Promising Hydrogen Storage Metal Organic Frameworks

Using first principles calculations, we show the high hydrogen storage capacity of metallacarboranes, where the transition metal (TM) atoms can bind up to 5 H-2-molecules. The average binding energy of similar to 0.3 eV/H favorably lies within the reversible adsorption range. Among the first row TM atoms, Sc and Ti are found to be the optimum in maximizing the H-2 storage (similar to 8 wt %) on the metallacarborane cluster. Being an integral part of the cage, TMs do not suffer from the aggregation problem, which has been the biggest hurdle for the success of TM-decorated graphitic materials for hydrogen storage. Furthermore, the presence of carbon atom in the cages permits linking the metallacarboranes to form metal organic frameworks, which are thus able to adsorb hydrogen via Kubas interaction, in addition to van der Waals physisorption.

Sonochemical synthesis of Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta nanocrystallites: oxygen storage material, CO oxidation and water gas shift catalyst

Nanocrystalline Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta of similar to 4 nm sizes were synthesized by a sonochemical method using diethyletriamine (DETA) as a complexing agent. Compounds were characterized by powder X-ray diffraction (XRD), X-ray photo-electron spectroscopy (XPS) and transmission electron microscopy (TEM). Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta crystallize in fluorite structure where Fe is in +3, Ce is in +4 and Pd is in +2 oxidation state. Due to substitution of smaller Fe3+ ion in CeO2, lattice oxygen is activated and 33% Fe substituted CeO2 i.e. Ce0.67Fe0.33O1.835 reversibly releases 0.31O] up to 600 degrees C which is higher or comparable to the oxygen storage capacity of CeO2-ZrO2 based solid solutions (Catal. Today 2002, 74, 225-234). Due to interaction of redox potentials of Pd2+/0(0.89 V) and Fe3+/2+ (0.77 V) with Ce4+/3+ (1.61 V), Pd ion accelerates the electron transfer from Fe2+ to Ce4+ in Ce0.65Fe0.33Pd0.02O1.815, making it a high oxygen storage material as well as a highly active catalyst for CO oxidation and water gas shift reaction. The activation energy for CO oxidation with Ce0.65Fe0.33Pd0.02O1.815 is found to be as low as 38 kJ mol(-1). Ce0.67Fe0.33O1.835 and Ce0.65Fe0.33Pd0.02O1.815 have also shown high activity for the water gas shift reaction. CO conversion to CO2 is 100% H-2 specific with these catalysts and conversion rate was found to be as high 27.2 mu moles g(-1) s(-1) and the activation energy was found to be 46.4 kJ mol(-1) for Ce0.65Fe0.33Pd0.02O1.815.

Power Management and Data Rate Maximization in Wireless Energy Harvesting Sensors

This paper considers the problem of power management and throughput maximization for energy neutral operation when using Energy Harvesting Sensors (EHS) to send data over wireless links. It is assumed that the EHS are designed to transmit data at a constant rate (using a fixed modulation and coding scheme) but are power-controlled. A framework under which the system designer can optimize the performance of EHS when the channel is Rayleigh fading is developed. For example, the highest average data rate that can be supported over a Rayleigh fading channel given the energy harvesting capability, the battery power storage efficiency and the maximum allowed transmit energy per slot is derived. Furthermore, the optimum transmission scheme that guarantees a particular data throughput is derived. The usefulness of the framework developed is illustrated through simulation results for specific examples.