Understanding the Reaction Mechanism of Nanocomposite Thermites

Nanocomposite energetics are a relatively new class of materials that combine nanoscale fuels and oxidizers to allow for the rapid release of large amounts of energy. In thermite systems (metal fuel with metal oxide oxidizer), the use of nanomaterials has been illustrated to increase reactivity by multiple orders of magnitude as a result of the higher specific surface area and smaller diffusion length scales. However, the highly dynamic and nanoscale processes intrinsic to these materials, as well as heating rate dependencies, have limited our understanding of the underlying processes that control reaction and propagation. For my dissertation, I have employed a variety of experimental approaches that have allowed me to probe these processes at heating rates representative of free combustion with the goal of understanding the fundamental mechanisms. Dynamic transmission electron microscopy (DTEM) was used to study the in situ morphological change that occurs in nanocomposite thermite materials subjected to rapid (10^11 K/s) heating. Aluminum nanoparticle (Al-NP) aggregates were found to lose their nanostructure through coalescence in as little as 10 ns, which is much faster than any other timescale of combustion. Further study of nanoscale reaction with CuO determined that a condensed phase interfacial reaction could occur within 0.5-5 µs in a manner consistent with bulk reaction, which supports that this mechanism plays a dominant role in the overall reaction process. Ta nanocomposites were also studied to determine if a high melting point (3280 K) affects the loss of nanostructure and rate of reaction. The condensed phase reaction pathway was further explored using reactive multilayers sputter deposited onto thin Pt wires to allow for temperature jump (T-Jump) heating at rates of ~5x10^5 K/s. High speed video and a time of flight mass spectrometry (TOFMS) were used to observe ignition temperature and speciation as a function of bilayer thickness. The ignition process was modeled and a low activation energy for effective diffusivity was determined. T-Jump TOFMS along with constant volume combustion cell studies were also used to determine the effect of gas release in nanoparticle systems by comparing the reaction properties of CuO and Cu2O.

Controlling Nanostructures for in-situ TEM Characterization

Low dimensional nanostructures, such as nanotubes and 2D sheets, have unique and promising material properties both from a fundamental science and an application standpoint. Theoretical modelling and calculations predict previously unobserved phenomena that experimental scientists often struggle to reproduce because of the difficulty in controlling and characterizing the small structures under real-world constraints. The goal of this dissertation is to controlling these structures so that nanostructures can be characterized in-situ in transmission electron microscopes (TEM) allowing for direct observation of the actual physical responses of the materials to different stimuli. Of most interest to this work are the thermal and electrical properties of carbon nanotubes, boron nitride nanotubes, and graphene. The first topic of the dissertation is using surfactants for aqueous processing to fabricate, store, and deposit the nanostructures. More specifically, thorough characterization of a new surfactant, ammonium laurate (AL), is provided and shows that this new surfactant outperforms the standard surfactant for these materials, sodium dodecyl sulfate (SDS), in almost all tested metrics. New experimental set-ups have been developed by combining specialized in-situ TEM holders with innovative device fabrication. For example, electrical characterization of graphene was performed by using an STM-TEM holder and depositing graphene from aqueous solutions onto lithographically patterned, electron transparent silicon nitride membranes. These experiments produce exciting information about the interaction between graphene and metal probes and the substrate that it rests on. Then, by adding indium to the backside of the membrane and employing the electron thermal microscopy (EThM) technique, the same type of graphene samples could be characterized for thermal transport with high spatial resolution. It is found that reduced graphene oxide sheets deposited onto a silicon nitride membrane and displaying high levels of wrinkling have higher than expected electrical and thermal conduction properties. We are clearly able to visualize the ability of graphene to spread heat away from an electronic hot spot and into the substrate.

Ceramic Materials Development for Intermediate Temperature Solid Oxide Fuel Cell (IT-SOFC)

Solid oxide fuel cell (SOFC) is an electrochemical device that converts chemical energy into electric power with high efficiency. Traditional SOFC has its disadvantages, such as redox cycling instability and carbon deposition while using hydrocarbon fuels. It is because traditional SOFC uses Ni-cermet as anode. In order to solve these problems, ceramic anode is a good candidate to replace Ni. However, the conductivity of most ceramic anode materials are much lower than Ni metal, and it introduces high ohmic resistance. How to increase the conductivity is a hot topic in this research field. Based on our proposed mechanism, several types of ceramic materials have been developed. Vanadium doped perovskite, Sr1-x/2VxTi1-xO3 (SVT) and Sr0.2Na0.8Nb1-xVxO3 (SNNV), achieved the conductivity as high as 300 S*cm-1 in hydrogen, without any high temperature reduction. GDC electrolyte supported cell was fabricated with Sr0.2Na0.8Nb0.9V0.1O3 and the performance was measured in hydrogen and methane respectively. Due to vanadium’s intrinsic problems, the anode supported cell is not easy. Fe doped double perovskite Sr2CoMoO6 (SFCM) was also developed. By carefully doping Fe, the conductivity was improved over one magnitude, without any vigorous reducing conditions. SFCM anode supported cell was successfully fabricated with GDC as the electrolyte. By impregnating Ni-GDC nano particles into the anode, the cell can be operated at lower temperatures while having higher performance than the traditional Ni-cermet cells. Meanwhile, this SFCM anode supported SOFC has long term stability in the reformate containing methane. During the anode development, cathode improvement caused by a thin Co-GDC layer was observed. By adding this Co-GDC layer between the electrolyte and the cathode, the interfacial resistance decreases due to fast oxygen ion transport. This mechanism was confirmed via isotope exchange. This Co-GDC layer works with multiple kinds of cathodes and the modified cell’s performance is 3 times as the traditional Ni-GDC cell. With this new method, lowering the SOFC operation temperature is feasible.

Characterization of Copper Covetic Bulk and Films: Copper with High Carbon Content

Incorporation of carbon nanostructures in metals is desirable to combine the strongly bonded electrons in the metal and the free electrons in carbon nanostructures that give rise to high ampacity and high conductivity, respectively. Carbon in copper has the potential to impact industries such as: building construction, power generation and transmission, and microelectronics. This thesis focuses on the structure and properties of bulk and thin films of a new material, Cu covetic, that contains carbon in concentrations up to 16 at.%. X-ray photoelectron spectroscopy (XPS) shows C 1s peak with both sp2 and sp3 bonded C measuring up to 3.5 wt.% (16 at.%). High resolution transmission electron microscopy and electron diffraction of bulk covetic samples show a modulated structure of ≈ 1.6 nm along several crystallographic directions in regions that have high C content suggesting that the carbon incorporates into the copper lattice forming a network. Electron energy loss spectra (EELS) from covetics reveal that the level of graphitization from the source material, activated carbon, is maintained in the covetic structure. Bulk Cu covetics have a slight increase in the lattice constant, as well as <111> texturing, or possibly a different structure, compared to pure Cu. Density functional theory calculations predict bonding between C and Cu at the edges and defects of graphene sheets. The electrical resistivity of bulk covetics first increases and then decreases with increasing C content. Cu covetic films were deposited using e-beam and pulsed laser deposition (PLD) at different temperatures. No copper oxide or any allotropes of carbon are present in the films. The e-beam films show enhanced electrical and optical properties when compared to pure Cu films of the same thickness even though no carbon was detected by XPS or EELS. They also have slightly higher ampacity than Cu metal films. EELS analysis of the C-K-edge in the PLD films indicate that graphitic carbon is transferred from the bulk into the films with uniform carbon distribution. PLD films exhibit flatter and higher transmittance curves and sheet resistance two orders of magnitude lower than e-beam films leading to a high figure of merit as transparent conductors.

Nano-Engineering of Densely Packed Electrochemical Energy Storage Architectures by Atomic Layer Deposition

Nanostructures are highly attractive for future electrical energy storage devices because they enable large surface area and short ion transport time through thin electrode layers for high power devices. Significant enhancement in power density of batteries has been achieved by nano-engineered structures, particularly anode and cathode nanostructures spatially separated far apart by a porous membrane and/or a defined electrolyte region. A self-aligned nanostructured battery fully confined within a single nanopore presents a powerful platform to determine the rate performance and cyclability limits of nanostructured storage devices. Atomic layer deposition (ALD) has enabled us to create and evaluate such structures, comprised of nanotubular electrodes and electrolyte confined within anodic aluminum oxide (AAO) nanopores. The V2O5- V2O5 symmetric nanopore battery displays exceptional power-energy performance and cyclability when tested as a massively parallel device (~2billion/cm2), each with ~1m3 volume (~1fL). Cycled between 0.2V and 1.8V, this full cell has capacity retention of 95% at 5C rate and 46% at 150C, with more than 1000 charge/discharge cycles. These results demonstrate the promise of ultrasmall, self-aligned/regular, densely packed nanobattery structures as a testbed to study ionics and electrodics at the nanoscale with various geometrical modifications and as a building block for high performance energy storage systems[1, 2]. Further increase of full cell output potential is also demonstrated in asymmetric full cell configurations with various low voltage anode materials. The asymmetric full cell nanopore batteries, comprised of V2O5 as cathode and prelithiated SnO2 or anatase phase TiO2 as anode, with integrated nanotubular metal current collectors underneath each nanotubular storage electrode, also enabled by ALD. By controlling the amount of lithium ion prelithiated into SnO2 anode, we can tune full cell output voltage in the range of 0.3V and 3V. This asymmetric nanopore battery array displays exceptional rate performance and cyclability. When cycled between 1V and 3V, it has capacity retention of approximately 73% at 200C rate compared to 1C, with only 2% capacity loss after more than 500 charge/discharge cycles. With increased full cell output potential, the asymmetric V2O5-SnO2 nanopore battery shows significantly improved energy and power density. This configuration presents a more realistic test - through its asymmetric (vs symmetric) configuration – of performance and cyclability in nanoconfined environment. This dissertation covers (1) Ultra small electrochemical storage platform design and fabrication, (2) Electron and ion transport in nanostructured electrodes inside a half cell configuration, (3) Ion transport between anode and cathode in confined nanochannels in symmetric full cells, (4) Scale up energy and power density with geometry optimization and low voltage anode materials in asymmetric full cell configurations. As a supplement, selective growth of ALD to improve graphene conductance will also be discussed[3]. References: 1. Liu, C., et al., (Invited) A Rational Design for Batteries at Nanoscale by Atomic Layer Deposition. ECS Transactions, 2015. 69(7): p. 23-30. 2. Liu, C.Y., et al., An all-in-one nanopore battery array. Nature Nanotechnology, 2014. 9(12): p. 1031-1039. 3. Liu, C., et al., Improving Graphene Conductivity through Selective Atomic Layer Deposition. ECS Transactions, 2015. 69(7): p. 133-138.