Solid electrolyte materials have the potential to improve performance and safety characteristics of lithium-ion batteries by replacing conventional solvent-based electrolytes. A candidate solid polymer electrolyte, AMLi/PEGDM, has been synthesized by crosslinking an anionic monomer AMLi, with poly(ethylene glycol) dimethacrylate. The main goal of the synthesis is to produce a single-ion conducting polymer network where lithium cations can move freely and fluorinated anions are immobilized as part of the polymer network. A comprehensive characterization of anion and cation mobility in the resulting material is therefore required. Using pulsed-field gradient nuclear magnetic resonance (PFG-NMR), we are able to measure and quantify the individual diffusion coefficients of mobile species in the material (19F and 7Li) and confirm the extent to which the fluorinated anionic component is immobilized. We have characterized dry (σ~3.0 x10-7 S/cm at 30°C) and propylene carbonate (PC) saturated gel (σ~1.0x10-4 S/cm at 30°C) samples. Experimental results include NMR spin-spin and spin-lattice relaxation times in addition to diffusion coefficient measurements over a temperature range up to 100°C. Practically, the diffusion measurements are extremely challenging, as the spin-spin (T2) relaxation times are very short, necessitating the development of specialized pulsed-field gradient apparatus. Diffusion coefficients for the most mobile components of the lithium cations and fluorinated anions at 100°C in dry membranes have been found to be 3.4 x10-8 cm2/s and 2.1 x10-8 cm2/s respectively. These results provide valuable insight into the conduction mechanisms in these materials, and will drive further optimization of solid polymer electrolytes.

We report on the use of in-situ small angle neutron scattering (SANS) technique to study the phase behavior of hydrogen confined in narrow pores of ultramicroporous carbon (UMC) with a very large surface area (2630 m2/g) and pore volume (1.3 cm3/g). The effect of pore size and pressure on hydrogen adsorbed on UMC at room temperature and pressures up to ∼200 bar were investigated. In a previous experiment, we have measured the density of adsorbed H2 gas in the nanopores and mesopores of polyfurfuryl alcohol-derived activated carbon (PFAC) by SANS technique. Here, a comparative SANS study between the UMC and PFAC was conducted in order to further investigate the densification of H2 as a function of pore size and pressure. Initial results suggest that the density of confined H2 in both UMC and PFAC is considerably higher than that of the bulk hydrogen gas. The density is systematically higher in the narrow pores and decreases with increasing pore size. These results clearly demonstrate the advantage of adsorptive storage over compressed gas storage and emphasize the greater efficiency of micropores over mesopores in the adsorption process, which can be used to guide the development of new carbon adsorbents tailored for maximum H2 storage capacities at near-ambient temperatures.

Li2FeP2O7 is a newly developed polyanionic cathode material for high performance lithium ion batteries. It is considered very attractive due to its large specific capacity, good thermal and chemical stability, and environmental benignity. However, the application of Li2FeP2O7 is limited by its low ionic and electronic conductivities. To overcome the above problem, a solution-based technique was successfully developed to synthesize Li2FeP2O7 powders with very fine and uniform particle size (< 1 μm), achieving much faster kinetics. The obtained Li2FeP2O7 powders were tested in lithium ion batteries by measurements of cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge/discharge cycling. We found that the modified Li2FeP2O7 cathode could maintain a relatively high capacity even at fast discharge rates.

The relationship between tortuosity and porosity and its influence on effective transport properties in lithium-ion cells was analyzed. The variation in cell performance with changes in component thicknesses, porosities and tortuosities was investigated. Optimal, novel electrode designs are developed to improve their rate capability even at higher active material loadings.

Graphene-based all-solid-state supercapacitors the using ionic liquid gel polymer electrolyte have been fabricated and characterized. The gel polymer electrolyte has been prepared by immobilizing ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF4) with poly(vinylidene fluoride-hexafluoropropylene). Cyclic voltammetry studies show highly capacitive behavior under fast scan rates. Impedance analysis show nominal charge transfer and ion diffusion at pores related resistance contributions. The graphene-based solid-state supercapacitor shows optimum capacitance of 80 mF cm-2 (equivalent to the single electrode specific capacitance of 76 F g-1). This corresponded to the specific energy of 7.4 Wh kg-1 and specific power of 4.5 kW kg-1. The supercapacitor cell shows stable cyclic performances for up to 5000 cycles and possibly beyond.

Sustainable energy is currently limited by the ability of materials to store energy and deliver it on demand. Allotropes of carbon are attractive for their potential for use in energy storage due to low weight, high chemical stability and low production cost. Carbon nanotubes and graphene can be combined to provide an effective three-dimensional material with high conductivity and high surface area. We demonstrate the use of block copolymers to obtain patterned arrays of iron nanoparticles which give rise to ordered carbon nanotubes with good size distribution. A one-step chemical vapor deposition process for large-area fabrication of the graphene and carbon nanotube hybrid structure is described. Following chemical vapor deposition the hybrid material is demonstrated in a supercapacitor device. The fabricated supercapacitor exhibits high electrical conductivity, and has potential for extremely high energy storage capability.

High quality garnet-type Li7La3Zr2O12 solid electrolyte was synthesized using a solution-based technique. The electrolyte pellets were sintered at 900 oC, resulting in tetragonal phase, which then transformed to cubic phase after annealing at 1230 oC. The ionic conductivity of both phases was studied and revealed to be 3.67x10-7 S/cm and 1.67×10-4 S/cm, respectively. A proto-type cell comprising of Li7La3Zr2O12 electrolyte, LiCoO2 cathode and lithium metal anode was assembled. The cell made with the cubic phase electrolyte exhibited superior performance than the one made with the tetragonal phase electrolyte. The former cell possessed a very promising gravimetric discharge capacity of 3.4 mAh/g, which is the highest value obtained among similar setups.

We proposed the use of Copper (Cu) and Zinc (Zn) nanoparticles as the electrodes for thin-film microbatteries in the applications of micro-scale sensors. Compared to the widely used lithium-based batteries, Cu and Zn nanoparticles are less expensive, less prone to oxidation (thus involving simpler fabrication steps) and flammability, safe to use, and only requires very simple fabrication processes.Even though the voltage output is inherently smaller (∼1V) than conventional lithium-based batteries, it is sufficient for low-voltage Integrated Circuits (IC) technologies such as 130 nm and 90 nm channel length transistor processes.

Commercial paper will be used as the separator to demonstrate the battery capacity. Paper that acts as the separator is slurry-casted with nanoparticles (30-40 nm in size) on both sides. The thickness of the metal nanoparticles-coated thin films and the paper separator are 1 μm and 100 μm, respectively.

The electrodes were developed to achieve high conductivity (lower than 1 (Ω·cm)-1) with smooth surface, good adhesion, and flexibility. The metal nanoparticles will be formulated to slurry solutions for screen printing or ink-jet printing for the battery fabrication. For fabrication purposes, the slurries viscosity is approximately in the range of 10-12 cPs at the operating temperature, a surface tension between 28-33 dynes/cm. During the fabrication process including printing/coating and sintering, reductive environment is required to minimize the oxidation. AFM (Atomic Force Microscopy) and EDS (Energy Dispersive Spectroscopy) results will be employed to demonstrate the surface morphology as well as the percentages of metal oxides. Batteries will be tested with and without an ionic liquid for comparison. Humidity effects on the battery performance will also be discussed.

Different geometries that are designed to make the batteries with higher voltage or charge will be proposed. Characterization results will include the open-circuit voltage, dielectric property, charging and discharging curve, capacitance and capacity, AFM of the surface test, EDS of the electrodes and the SEM (Scanning Electron microscopy) of the particles.Ourresearch suggest that conductive paper can be scalable and could make high-performance energy storage and conversion devices at low cost and would bring new opportunities for advanced applications.

Carbon nanotube-spinel lithium titanate (CNT-Li4Ti5O12) nanoparticles have been synthesized by hydrothermal reaction and higher-temperature calcinations with LiOH·H2O and TiO2 precursors in the presence of carbon nanotubes sources. The CNT-Li4Ti5O12 nanoparticles have been characterized by X-ray diffraction (XRD), high angle annular dark field (HAADF) images, and selected area electron diffraction (SAED). The particles exhibited a spinel cubic crystal phase and homogenous size distribution, with sizes around 50-70 nm. HAADF imaging confirmed that carbon content exists on the surface of the CNT-Li4Ti5O12 nanoparticles with graphitic carbon coating of 3-5 nm thickness under 800oC in the Ar gas. The graphitic carbon phase was further confirmed with Raman spectroscopy analysis on powder samples. Electrochemical characteristics were evaluated with galvanostatic discharge/charge tests, which showed that the initial discharge capacity is 172 mA·h/g at 0.1C. The nanoscale carbon layers uniformly coated the particles, and the interconnected carbon nanotube network is responsible for the improved charge rate capability and conductivity.

A phase field model is developed to investigate the formation of a solid electrolyte interface layer on the anode surface in lithium-ion batteries. Numerical results show that the growth of solid electrolyte interface exhibits power-law scaling with respect to time, and the growth rate depends on various factors such as temperature, diffusivity of electrons, and rates of electrochemical reactions.

Olivine lithium manganese phosphate, LiMnPO4 is a promising cathode material for high energy and safe lithium ion batteries. However, LiMnPO4 possesses excessively poor electrochemical activity, compared to conventional cathode materials. To enhance the electrochemical activity, we have synthesized LiMnPO4/multi-walled carbon nanotube (MWCNT) composites by employing an in-situ sol-gel method. The LiMnPO4/MWCNT composites were investigated by utilizing X-ray diffraction, thermogravimetric analysis, scanning electron microscope, transmission electron microscope, and galvanostatic charge-discharge cycling. The LiMnPO4 showed a particle size of ca. 50 nm and capacity of 102 mAh/g at 0.1 C without C.V. charging mode. This study demonstrated that the electrochemical activity of LiMnPO4 was significantly affected by not only pH and the amount of a chelating agent but also unreacted Mn2+. This is the first report analyzing the existence and effects of unreacted Mn2+ in LiMnPO4 synthesized by a sol-gel method.

In this work, we demonstrate a new density modulated multilayered silicon thin film anode approach that can provide a robust high capacity electrode for Li-ion batteries. These films have the ability to tolerate large volume changes due to their controlled microstructure. Silicon films with alternating layers of high/low material density were deposited using a DC sputtering system. Density of the individual layers was controlled by simply changing the working gas pressure during sputtering. Samples of Si films having thicknesses of 460 nm with different number of high/low density layers have been deposited on Cu current collectors. The electrochemical performance of the multilayered anode material was evaluated using a galvanostatic battery testing system at C/10 rate. After reaching a stabilized phase the battery cell showed a high coulombic efficiency of 96% to 99% and reversible specific capacity of 666 mAh g-1 (after 100 cycles). Low-density layers are believed to be acting as compliant sheets during volume expansion making the films more durable compared to conventional Si film anodes. The results indicate that density modulated multilayer Si thin films can be used to improve the mechanical properties of Li-ion battery anodes leading to high reversible capacity values even after high number of cycles.

We investigate the electronic structure of interstitial Li and Li vacancy in Li10GeP2S12 by first principles calculations. We find that the Li vacancy and interstitial Li+ ion do not introduce states in the band gap hence they do not deteriorate the electronic properties of Li10GeP2S12. The energy barrier for Li interstitial diffusion in Li10GeP2S12 is estimated to be 1.4 eV, which is much larger than that of the Li vacancy in Li10GeP2S12. This fact suggests that the ion conductivity arises from the migration of Li vacancy.