Investigation of Spillover Effect to Enhance Hydrogen Storage

Hydrogen is an attractive energy option because of its lowenvironmental impact, but a critical problem is its low energydensity, which makes it difficult to store. For example, the USDepartment of Energy (DOE) hydrogen plan for fuel cell poweredvehicles requires a gravimetric density of 6.5 wt%. There are severalexisting hydrogen storage methods, including compressed gas,liquefaction, metal hydrides, and physisorption, but at present, noneof these technologies comes close to achieving the targets set by theDOE. Although chemical storage methods have been claimed to be themost promising hydrogen storage technology, and activated carbons thebest adsorbent, as mentioned, chemical storage methods are still farfrom the desired targets. In order to try to bring these chemicalstorage methods closer to desired targets, research must be done tofind ways to maximize chemical storage potential using differentmaterials. Recently, there has been a resurgence of interest in thepotential of carbon materials. In order to try to move these hydrogenstorage goals further toward the goals of the DOE, numerousexperiments were done in altering the current materials to try tomaximize the hydrogen storage potential. Hydrogen Spillover, onemethod currently being considered, is where a metal catalystdissociates hydrogen molecules into atomic hydrogen, which thenmigrates down toward the carbon surface and is adsorbed onto thecarbon receptor. Experiments were done to compare the spillovereffects of multiple precious metals. Also, the use of basic highsurface area activated carbon (MSC-30) was compared to similaractivated carbons with Boron doping, with hopes of seeing anenhancement of that spillover effect. Unfortunately, no significantincreases on the current storage capacity via spillover of ~1.2wt%were achieved

Evaluation of Hydrogen Storage in Metal Organic Frameworks by Bridged Hydrogen Spillover

Hydrogen has the potential to be the next energy carrier. The ability to use hydrogen in fuel cell technologies depends largely on the ability to store hydrogen efficiently. Metal-Organic Frameworks (MOFs) belong to an interesting set of materials that consists of porous channels and have been shown to carry potential for hydrogen storage when added to metal catalysts. MOFs alone show no potential to store hydrogen, but when added to metal catalyst they can exhibit a spillover effect to increase hydrogen storage capacity. The key critical issues with MOFs are to validate the promises that MOFs can provide with spillover, since spillover intricately linked to more standard H2 storage mechanisms. The current project focuses on the synthesis of Isoreticular Metal Organic Framework-8 (IRMOF-8) added to platinum on Activated Carbon (AC) and bridged together with sucrose to enhance the spillover effect. In order to reach hydrogen storage goals, a method must be proven to have enough capacity for the adsorption/resorption (reversibility) at ambient and 120 bar reasonable pressures. With the tremendous interest in spillover materials for hydrogen storage, NREL and DOE have dedicated resources to synthesize specific materials and to develop, perform, and validate the requisite measurements

Single Wall Carbon Nanotube-polymer Solar Cells

Investigation of single wall carbon nanotube (SWNT)-polymer solar cells has been conducted towards developing alternative lightweight, flexible devices for space power applications. Photovoltaic devices were constructed with regioregular poly(3-octylthiophene)-(P3OT) and purified, >95% w/w, laser-generated SWNTs. The P3OT composites were deposited on ITO-coated polyethylene terapthalate (PET) and I-V characterization was performed under simulated AM0 illumination. Fabricated devices for the 1.0% w/w SWNT-P3OT composites showed a photoresponse with an open-circuit voltage (V(sub oc)) of 0.98 V and a short-circuit current density (I(sub sc)) of 0.12 mA/sq cm. Optimization of carrier transport within these novel photovoltaic systems is proposed, specifically development of nanostructure-SWNT complexes to enhance exciton dissociation

Developing new functional TCs

Transparent Conductors (TCs) are increasingly critical to the performance and reliability of a number of technologies. Traditionally based primarily on oxides of Ga, In, Zn and Sn the class is rapidly expanding into new materials including both other oxides and more recently composites of metallic or carbon nanowires. Many of these materials offer unique functionality as well as processing and reliability advantages over some of the historic materials. These compounds are all classically non-stoiciometric and often metastable consisting of oxide, non-oxide and composite materials which are being collectively looked at for an increasingly broad set of applications including photovoltaics, solid state lighting, power electronics and a broad class of flexible and wearable electronics. In this talk, we will focus on two main areas; the development of predictive models to be able to identify dopants and the processing regimes where they can be activated as well as the use of nanowire oxide composites to develop a new generation of tunable high performance TC. The complex set of demands for a desired TC include not only classical performance, but also processibility, cost and reliability necessitating a search for new materials. The ability to use materials genomics to identify new dopable TC materials that are experimentally realizable is rapidly increasing. We will discuss recent work on predicting the dopability of Ga2O3 films, which potentially have broad applicability as buffer layers, TCOs, and in power electronics if the doping level can be well controlled. We will discuss the theoretical predictions for the process windows to activate both Sn and Si as dopants and compare this to experimental results and the literature. We will also present resent results on the theoretical prediction and realization of a new p-type TC based on CuZnS, which has demonstrated conductivities of up to 100 S/cm. The latter while not classically an oxide is certainly non-stoichiometric and properties are enhanced in many cases by the use of complex oxide, sulfide and selenide materials. Together these will illustrate the evolving tools both theory and experiment to develop and realize dopants in wide band gap materials. In cases where single materials may not be sufficient, nanowire (metal or carbon based) composites with oxides is increasingly attractive. For example, Ag, and potentially Cu, nanowires embedded in a metal oxide matrix can potentially produce TCs that can be processed at low temperature, have conductivity and transparency comparable to the best TCOs, control interface stability and electronic properties and are suitable to flexible electronics. We will present work on ZnO, InZnO and ZnSnO composites with Ag nanowires where the performance can be as good as high quality InSnO with films Rs\u3c 10 Ohms/sq. We will discuss the dependence on the interrelationship between the nanowire properties and the oxide properties. We will also discus the concept of employing sandwich oxides to separately optimize the top and bottom interfacial properties. This work was supported, in part, by the Center for the Next Generation of Materials by Design, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. This research also supported in part by the Solar Energy Research Institute for India and the U.S. (SERIIUS) funded jointly by the U.S. Department of Energy subcontract DE AC36-08G028308 (Office of Science, Office of Basic Energy Sciences, and Energy Efficiency and Renewable Energy, Solar Energy Technology Program, with support from the Office of International Affairs) and the Government of India subcontract IUSSTF/JCERDC-SERIIUS/2012 dated 22nd Nov. 2012

Thermionic Emission of Single-Wall Carbon Nanotubes Measured

Researchers at the NASA Glenn Research Center, in collaboration with the Rochester Institute of Technology, have investigated the thermionic properties of high-purity, single-wall carbon nanotubes (SWNTs) for use as electron-emitting electrodes. Carbon nanotubes are a recently discovered material made from carbon atoms bonded into nanometer-scale hollow tubes. Such nanotubes have remarkable properties. An extremely high aspect ratio, as well as unique mechanical and electronic properties, make single-wall nanotubes ideal for use in a vast array of applications. Carbon nanotubes typically have diameters on the order of 1 to 2 nm. As a result, the ends have a small radius of curvature. It is these characteristics, therefore, that indicate they might be excellent potential candidates for both thermionic and field emission

Research and development of hydrogen carrier based solutions for hydrogen compression and storage

publishedVersio

Fundamentals of hydrogen storage in nanoporous materials

Physisorption of hydrogen in nanoporous materials offers an efficient and competitive alternative for hydrogen storage. At low temperatures (e.g. 77 K) and moderate pressures (below 100 bar) molecular H2 adsorbs reversibly, with very fast kinetics, at high density on the inner surfaces of materials such as zeolites, activated carbons and metal–organic frameworks (MOFs). This review, by experts of Task 40 ‘Energy Storage and Conversion based on Hydrogen’ of the Hydrogen Technology Collaboration Programme of the International Energy Agency, covers the fundamentals of H2 adsorption in nanoporous materials and assessment of their storage performance. The discussion includes recent work on H2 adsorption at both low temperature and high pressure, new findings on the assessment of the hydrogen storage performance of materials, the correlation of volumetric and gravimetric H2 storage capacities, usable capacity, and optimum operating temperature. The application of neutron scattering as an ideal tool for characterising H2 adsorption is summarised and state-of-the-art computational methods, such as machine learning, are considered for the discovery of new MOFs for H2 storage applications, as well as the modelling of flexible porous networks for optimised H2 delivery. The discussion focuses moreover on additional important issues, such as sustainable materials synthesis and improved reproducibility of experimental H2 adsorption isotherm data by interlaboratory exercises and reference materials

Physi-Sorption of H2 on Pure and Boron–Doped Graphene Monolayers: A Dispersion–Corrected DFT Study

High-surface-area carbons are of interest as potential candidates to store H2 for fuel–cell power applications. Earlier work has been ambiguous and inconclusive on the effect of boron doping on H2 binding energy. Here, we describe a systematic dispersion–corrected density functional theory study to evaluate the effect of boron doping. We observe some enhancement in H2 binding, due to the presence of a defect, such as terminal hydrogen or distortion from planarity, introduced by the inclusion of boron into a graphene ring, which creates hydrogen adsorption sites with slightly increased binding energy. The increase is from −5 kJ/mol H2 for the pure carbon matrix to −7 kJ/mol H2 for the boron–doped system with the boron content of ~7%. The H2 binding sites have little direct interaction with boron. However, the largest enhancement in physi-sorption energy is seen for systems, where H2 is confined between layers at a distance of about 7 Å, where the H2 binding nearly doubles to −11 kJ/mol H2. These findings suggest that interplanar nanoconfinement might be more effective in enhancing H2 binding. Smaller coronene model is shown to be beneficial for understanding the dependence of interaction energy on the structural configurations and preferential H2 binding sites

Relationship between Molecular Structure and Electron Transfer in a Polymeric Nitroxyl-Radical Energy Storage Material

In recent years, stable organic radical functional groups have been incorporated into a variety of polymeric materials for use as electrodes within energy storage devices, for example, batteries and capacitors. With the complex nature of the charge-transfer processes in a polymer matrix, the morphologies of the polymer films can have a significant impact on the redox behavior of the organic-based radical. To elucidate possible effects of packing on electron-transport mechanisms, theoretical modeling of the well-characterized cathode material poly­(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PTMA) was conducted. Polymer morphologies were modeled using classical molecular dynamics simulations, and subsequently, the electronic-coupling matrix element between each radical site was calculated. Building on a previously derived treatment of diffusion in inhomogeneous materials, an expression for an effective electron diffusion length and an effective electron diffusion rate was derived in terms of an electronic-coupling-weighted radial distribution function. Two primary distances were found to contribute to the effective electron transfer length of 5.5 Å with a majority of the electron transfer, nearly 85%, occurring between radical sites on different polymer chains. Finally, we point out that this analysis of charge transfer using an electronic-coupling-weighted radial distribution function has application beyond the specific system addressed here and that it may prove useful more generally for simulating electron-transfer processes in disordered molecular materials