STRAINING ENGINEERING OF GRAPHENE AND GRAPHENE-BASED NANOSTRUCTURES

Graphene has emerged as an extraordinary material with its capability to accommodate an array of remarkable electronic, mechanical and chemical properties. Extra-large surface-to-volume ratio renders graphene a highly flexible morphology, giving rise to intriguing observations such as ripples, wrinkles and folds as well as the potential to transform into other novel carbon nanostructures. Ultra-thin, mechanically tough, electrically conductive graphene films promise to enable a wealth of possible applications ranging from hydrogen storage scaffolds, electronic transistors, to bottom-up material designs. Enthusiasm for graphene-based applications aside, there are still significant challenges to their realization, largely due to the difficulty of precisely controlling the graphene properties. Controlling the graphene morphology over large areas is crucial in enabling future graphene-based applications and material design. This dissertation aims to shed lights on potential mechanisms to actively manipulate the graphene morphology and properties and therefore enable the material design principle that delivers desirable mechanical and electronic functionalities of graphene and its derivatives.

The controlled delivery of hydrogen sulfide for the preservation of heart tissue

Gemstone Team Organ Storage and Hibernation

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.

INVESTIGATION OF MAGNESIUM ION CHARGE STORAGE MECHANISM IN MANGANESE DIOXIDE

Magnesium (Mg) battery is considered as a promising candidate for the next generation battery technology that could potentially replace the current lithium (Li)-ion batteries due to the following factors. Magnesium possesses a higher volumetric capacity than commercialized Li-ion battery anode materials. Additionally, the low cost and high abundance of Mg compared to Li makes Mg batteries even more attractive. Moreover, unlike metallic Li anodes which have a tendency to develop a dendritic structure on the surface upon the cycling of the battery, Mg metal is known to be free from such a hazardous phenomenon. Due to these merits of Mg as an anode, the topic of rechargea¬ble Mg batteries has attracted considerable attention among researchers in the last few decades. However, the aforementioned advantages of Mg batteries have not been fully utilized due to the serious kinetic limitation of Mg2+ diffusion process in many hosting compounds which is believed to be due to a strong electrostatic interaction between divalent Mg2+ ions and hosting matrix. This serious kinetic hindrance is directly related to the lack of cathode materials for Mg battery that provide comparable electrochemical performances to that of Li-based system. Manganese oxide (MnO2) is one of the most well studied electrode materials due to its excellent electrochemical properties, including high Li+ ion capacity and relatively high operating voltage (i.e., ~ 4 V vs. Li/Li+ for LiMn2O4 and ~ 3.2 V vs. Mg/Mg2+). However, unlike the good electrochemical properties of MnO2 realized in Li-based systems, rather poor electrochemical performances have been reported in Mg based systems, particularly with low capacity and poor cycling performances. While the origin of the observed poor performances is believed to be due to the aforementioned strong ionic interaction between the Mg2+ ions and MnO2 lattice resulting in a limited diffusion of Mg2+ ions in MnO2, very little has been explored regarding the charge storage mechanism of MnO2 with divalent Mg2+ ions. This dissertation investigates the charge storage mechanism of MnO2, focusing on the insertion behaviors of divalent Mg2+ ions and exploring the origins of the limited Mg2+ insertion behavior in MnO2. It is found that the limited Mg2+ capacity in MnO2 can be significantly improved by introducing water molecules in the Mg electrolyte system, where the water molecules effectively mitigated the kinetic hindrance of Mg2+ insertion process. The combination of nanostructured MnO2 electrode and water effect provides a synergic effect demonstrating further enhanced Mg2+ insertion capability. Furthermore, it is demonstrated in this study that pre-cycling MnO2 electrodes in water-containing electrolyte activates MnO2 electrode, after which improved Mg2+ capacity is maintained in dry Mg electrolyte. Based on a series of XPS analysis, a conversion mechanism is proposed where magnesiated MnO2 undergoes a conversion reaction to Mg(OH)2 and MnOx and Mn(OH)y species in the presence of water molecules. This conversion process is believed to be the driving force that generates the improved Mg2+ capacity in MnO2 along with the water molecule’s charge screening effect. Finally, it is discussed that upon a consecutive cycling of MnO2 in the water-containing Mg electrolyte, structural water is generated within the MnO2 lattice, which is thought to be the origin of the observed activation phenomenon. The results provided in this dissertation highlight that the divalency of Mg2+ ions result in very different electrochemical behaviors than those of the well-studied monovalent Li+ ions towards MnO2.

MANIPULATION OF IONS, ELECTRONS, AND PHOTONS IN 2D MATERIALS BY ION INTERCALATION

2D materials have attracted tremendous attention due to their unique physical and chemical properties since the discovery of graphene. Despite these intrinsic properties, various modification methods have been applied to 2D materials that yield even more exciting results. Among all modification methods, the intercalation of 2D materials provides the highest possible doping and/or phase change to the pristine 2D materials. This doping effect highly modifies 2D materials, with extraordinary electrical transport as well as optical, thermal, magnetic, and catalytic properties, which are advantageous for optoelectronics, superconductors, thermoelectronics, catalysis and energy storage applications. To study the property changes of 2D materials, we designed and built a planar nanobattery that allows electrochemical ion intercalation in 2D materials. More importantly, this planar nanobattery enables characterization of electrical, optical and structural properties of 2D materials in situ and real time upon ion intercalation. With this device, we successfully intercalated Li-ions into few layer graphene (FLG) and ultrathin graphite, heavily dopes the graphene to 0.6 x 10^15 /cm2, which simultaneously increased its conductivity and transmittance in the visible range. The intercalated LiC6 single crystallite achieved extraordinary optoelectronic properties, in which an eight-layered Li intercalated FLG achieved transmittance of 91.7% (at 550 nm) and sheet resistance of 3 ohm/sq. We extend the research to obtain scalable, printable graphene based transparent conductors with ion intercalation. Surfactant free, printed reduced graphene oxide transparent conductor thin film with Na-ion intercalation is obtained with transmittance of 79% and sheet resistance of 300 ohm/sq (at 550 nm). The figure of merit is calculated as the best pure rGO based transparent conductors. We further improved the tunability of the reduced graphene oxide film by using two layers of CNT films to sandwich it. The tunable range of rGO film is demonstrated from 0.9 um to 10 um in wavelength. Other ions such as K-ion is also studied of its intercalation chemistry and optical properties in graphitic materials. We also used the in situ characterization tools to understand the fundamental properties and improve the performance of battery electrode materials. We investigated the Na-ion interaction with rGO by in situ Transmission electron microscopy (TEM). For the first time, we observed reversible Na metal cluster (with diameter larger than 10 nm) deposition on rGO surface, which we evidenced with atom-resolved HRTEM image of Na metal and electron diffraction pattern. This discovery leads to a porous reduced graphene oxide sodium ion battery anode with record high reversible specific capacity around 450 mAh/g at 25mA/g, a high rate performance of 200 mAh/g at 250 mA/g, and stable cycling performance up to 750 cycles. In addition, direct observation of irreversible formation of Na2O on rGO unveils the origin of commonly observed low 1st Columbic Efficiency of rGO containing electrodes. Another example for in situ characterization for battery electrode is using the planar nanobattery for 2D MoS2 crystallite. Planar nanobattery allows the intrinsic electrical conductivity measurement with single crystalline 2D battery electrode upon ion intercalation and deintercalation process, which is lacking in conventional battery characterization techniques. We discovered that with a “rapid-charging” process at the first cycle, the lithiated MoS2 undergoes a drastic resistance decrease, which in a regular lithiation process, the resistance always increases after lithiation at its final stage. This discovery leads to a 2- fold increase in specific capacity with with rapid first lithiated MoS2 composite electrode material, compare with the regular first lithiated MoS2 composite electrode material, at current density of 250 mA/g.

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.