Diagnostics and Degradation Investigations of Li-Ion Battery Electrodes using Single Nanowire Electrochemical Cells

Portable energy storage devices, which drive advanced technological devices, are improving the productivity and quality of our everyday lives. In order to meet the growing needs for energy storage in transportation applications, the current lithium-ion (Li-ion) battery technology requires new electrode materials with performance improvements in multiple aspects: (1) energy and power densities, (2) safety, and (3) performance lifetime. While a number of interesting nanomaterials have been synthesized in recent years with promising performance, accurate capabilities to probe the intrinsic performance of these high-performance materials within a battery environment are lacking. Most studies on electrode nanomaterials have so far used traditional, bulk-scale techniques such as cyclic voltammetry, electrochemical impedance spectroscopy, and Raman spectroscopy. These approaches give an ensemble-average estimation of the electrochemical properties of a battery electrode and does not provide a true indication of the performance that is intrinsic to its material system. Thus, new techniques are essential to understand the changes happening at a single particle level during the operation of a battery. The results from this thesis solve this need and study the electrical, mechanical and size changes that take place in a battery electrode at a single particle level. Single nanowire lithium cells are built by depositing nanowires in carefully designed device regions of a silicon chip using Dielectrophoresis (DEP). This work has demonstrated the assembly of several NW cathode materials like LiFePO4, pristine and acid-leached α-MnO2, todorokite – MnO2, acid and nonacid-leached Na0.44MnO2. Within these materials, α-MnO2 was chosen as the model material system for electrochemical experiments. Electrochemical lithiation of pristine α-MnO2 was performed inside a glove box. The volume, elasticity and conductivity changes were measured at each state-of-charge (SOC) to understand the performance of the material system. The NW size changes due to lithiation were measured using an Atomic Force Microscope (AFM) in the tapping mode. Electronic conductivity changes as a function of lithiation was also studied in the model α-MnO2 NWs and was found to decrease substantially with lithium loading. In other measurements involving a comparison between the alpha and todorokite phases of this material system, it was observed that the rate capability of these materials is limited not by the electronic but, by the ionic conductivity. Mechanical degradation of a battery cathode represents an important failure mode, which results in an irreversible loss of capacity with cycling. To analyze and understand these degradation mechanisms, this thesis has tested the evolution of nanomechanical properties of a battery cathode. Specifically, contact-mode AFM measurements have focused on the SOC-dependent changes in the Young’s modulus and fracture strength of an α-MnO2 NW electrode, which are critical parameters that determine its mechanical stability. These changes have been studied at the end of the first discharge step, 1 full electrochemical cycle, and 20 cycles. The observations show an increase in Young’s modulus at low concentrations of lithium loading and this is attributed to the formation of new Li-O bonds within the tunnel-structured cathode. As the lithium loading increases further, the Young’s modulus was observed to reduce and this is hypothesized to occur due to the distortions of the crystal at high lithium concentrations. The experimental-to-theoretical fracture strength ratio, which points to the defect density in the crystal at a given stoichiometry, was observed to reduce with electrochemical lithium insertion / cycling. This capability has demonstrated lithiation-dependent mechanical property measurements for the first time and represents an important contribution since degradation models, which are currently in use for materials at any size scale, always assume constant values regardless of the change in stoichiometry

Radio and Far-Infrared Emission as Tracers of Star Formation and AGN in Nearby Cluster Galaxies

We have studied the radio and far-infrared (FIR) emission from 114 galaxies in the 7 nearest clusters (<100 Mpc) with prominent X-ray emission to investigate the impact of the cluster environment on the star formation and AGN activity in the member galaxies. The X-ray selection criterion is adopted to focus on the most massive and dynamically relaxed clusters. A large majority of cluster galaxies show an excess in radio emission over that predicted from the radio-FIR correlation, the fraction of sources with radio excess increases toward cluster cores, and the radial gradient in the FIR/radio flux ratio is a result of radio enhancement. Of the radio-excess sources, 70% are early-type galaxies and the same fraction host an AGN. The galaxy density drops by a factor of 10 from the composite cluster center out to 1.5 Mpc, yet galaxies show no change in FIR properties over this region, and show no indication of mass segregation. We have examined in detail the physical mechanisms that might impact the FIR and radio emission of cluster galaxies. While collisional heating of dust may be important for galaxies in cluster centers, it appears to have a negligible effect on the observed FIR emission for our sample galaxies. The correlations between radio and FIR luminosity and radius could be explained by magnetic compression from thermal ICM pressure. We also find that simple delayed harassment cannot fully account for the observed radio, FIR, and mid-IR properties of cluster galaxies.Comment: 21 pages, 15 figures, Accepted by Ap

Synthesis, characterization, and application of magnetic gold nanoclusters

Au–Fe3O4 nanocomposites are of great interest for technological reasons due to their combined optical and magnetic properties. Nanosized Fe3O4 particles are superparamagnetic and can also be coated with a layer of Au, which supports localized plasmon resonances for useful optical properties. The dual properties of Au–Fe3O 4 nanoparticles have inspired chemists to design a variety of synthetic routes, some with good control of overall shape and size. However, most approaches require organic solvents, surfactants, or harsh chemical conditions. In this thesis we describe a simple and highly reproducible synthesis of magnetically active gold nanoclusters (MGNCs) with average particle sizes under 100 nm. This synthesis has two appealing features: (1) the synthesis is conducted entirely in water, with no amphiphilic surfactants that require subsequent removal, and (2) the chemical conditions used in MGNC synthesis are extremely mild, with minimum waste or by-products generated. The MGNCs can be used to support numerous applications in chemistry, biology, and materials science. In these thesis we describe two very different applications: (1) surface-modified chemical sensors based on surface-enhanced Raman scattering (SERS), for the detection of trace environmental pollutants such as tetrabromobisphenol A (TBBPA), and (2) magnetically guided “chisels” for the generation of nanosized channels in thermoplastic and glass films. The high aspect-ratio nanochannels were characterized by scanning electron microscopy and 3D confocal fluorescence imaging, and insights into the photothermal mechanism of nanopore generation were obtained by finite-element modeling simulations

Changing landscape of immuno-oncology: CAR-T therapy and PD1/PDL1 blockade

The current field of cancer treatment is undergoing a revolution. The influx of novel therapies derived from basic research on the immune system has shifted the landscape of modern medicine. Immunotherapy seeks to use the body’s own immune system as a medium to terminate neoplastic cells. This is performed by manipulating the immune system into either targeting cancer antigens or breaking down barriers towards T cell infiltration. The former mechanism uses CAR-T cells as an instrument to target specific cancer neo-antigens. CAR-T cells begin as T cells derived from a patient’s immune system. These cells are removed from the body and engineered to express a chimeric antigen receptor (CAR) through a process of viral transduction. This CAR allows the T cell to recognize and bind to a specific antigen of interest. In most cases, the antigen is present on cancer cells. The T cells, now expressing the CAR receptor, are transplanted back into the body of the patient and proceed to target cancer cells. This therapy has been used in hematological malignancies to great effect. Applying CAR-T cells to solid tumors is an ongoing process, but has been difficult to establish due to the immunosuppressive aspects of the tumor microenvironment. As such, combining CAR-T cells with traditional anti-cancer therapies has been proven to be efficacious in treating patients with solid tumors. In general, immunosuppression is a large problem in the treatment of cancer. Cancer cells and the tumor microenvironment express receptors that downregulate tumor-targeting actions of the immune system. The discovery of the programmed cell death protein 1 (PD1) allowed researchers to create novel antibodies that inhibit immunosuppression. PD1 located on T cells, binds to PDL1 on cancer and stromal cells. This interaction induces exhaustion and anergy in infiltrating T cells, thereby prevent T cells from targeting cancer cells. As such, the newly approved checkpoint blockade antibodies, Nivolumab and Pembrolizumab, block this interaction and allow T cells to carry out their targeting function. CAR-T cells and checkpoint blockade have both seen immense success in clinical trials and are currently being used the clinic. Nonetheless, development of these therapies for different types of cancers is an ongoing process and one that will require immense effort on behalf of the medical and pharmaceutical establishmen

Spectroscopic Measurements of the Far-Ultraviolet Dust Attenuation Curve at z~3

We present the first measurements of the shape of the far-ultraviolet (far-UV; lambda=950-1500 A) dust attenuation curve at high redshift (z~3). Our analysis employs rest-frame UV spectra of 933 galaxies at z~3, 121 of which have very deep spectroscopic observations (>7 hrs) at lambda=850-1300 A, with the Low Resolution Imaging Spectrograph on the Keck Telescope. By using an iterative approach in which we calculate the ratios of composite spectra in different bins of continuum color excess, E(B-V), we derive a dust curve that implies a lower attenuation in the far-UV for a given E(B-V) than those obtained with standard attenuation curves. We demonstrate that the UV composite spectra of z~3 galaxies can be modeled well by assuming our new attenuation curve, a high covering fraction of HI, and absorption from the Lyman-Werner bands of H2 with a small (<20%) covering fraction. The low covering fraction of H2 relative to that of the HI and dust suggests that most of the dust in the ISM of typical galaxies at z~3 is unrelated to the catalysis of H2, and is associated with other phases of the ISM (i.e., the ionized and neutral gas). The far-UV dust curve implies a factor of ~2 lower dust attenuation of Lyman continuum (ionizing) photons relative to those inferred from the most commonly assumed attenuation curves for L* galaxies at z~3. Our results may be utilized to assess the degree to which ionizing photons are attenuated in HII regions or, more generally, in the ionized or low column density (N(HI)<10^17.2 cm^-2) neutral ISM of high-redshift galaxies.Comment: 12 pages, 1 table, 8 figures, accepted to the Astrophysical Journa

A Glimpse of the First Galaxies

The recently refurbished Hubble Space Telescope reveals a galaxy from a time when the Universe was just 500 million years old, providing insights into the first throes of galaxy formation and the reionization of the Universe.Comment: Invited Nature "News and Views" Commentary on Bouwens et al. 2011, Nature, 469, 504-507; 5 pages, 1 figur

The Connection Between Reddening, Gas Covering Fraction, and the Escape of Ionizing Radiation at High Redshift

We use a large sample of galaxies at z~3 to establish a relationship between reddening, neutral gas covering fraction (fcov(HI)), and the escape of ionizing photons at high redshift. Our sample includes 933 galaxies at z~3, 121 of which have very deep spectroscopic observations (>7 hrs) in the rest-UV (lambda=850-1300 A) with Keck/LRIS. Based on the high covering fraction of outflowing optically-thick HI indicated by the composite spectra of these galaxies, we conclude that photoelectric absorption, rather than dust attenuation, dominates the depletion of ionizing photons. By modeling the composite spectra as the combination of an unattenuated stellar spectrum including nebular continuum emission with one that is absorbed by HI and reddened by a line-of-sight extinction, we derive an empirical relationship between E(B-V) and fcov(HI). Galaxies with redder UV continua have larger covering fractions of HI characterized by higher line-of-sight extinctions. Our results are consistent with the escape of Lya through gas-free lines-of-sight. Covering fractions based on low-ionization interstellar absorption lines systematically underpredict those deduced from the HI lines, suggesting that much of the outflowing gas may be metal-poor. We develop a model which connects the ionizing escape fraction with E(B-V), and which may be used to estimate the escape fraction for an ensemble of high-redshift galaxies. Alternatively, direct measurements of the escape fraction for our data allow us to constrain the intrinsic 900-to-1500 A flux density ratio to be >0.20, a value that favors stellar population models that include weaker stellar winds, a flatter initial mass function, and/or binary evolution. Lastly, we demonstrate how the framework discussed here may be used to assess the pathways by which ionizing radiation escapes from high-redshift galaxies. [Abridged]Comment: 22 pages, 3 tables, 14 figures, accepted to the Astrophysical Journa

X-Ray and Radio Emission from UV-Selected Star Forming Galaxies at Redshifts 1.5<Z<3.0 in the GOODS-North Field

We have examined the stacked radio and X-ray emission from UV-selected galaxies spectroscopically confirmed to lie between redshifts 1.5 < z < 3.0 in the GOODS-North field to determine their average extinction and star formation rates (SFRs). The X-ray and radio data are obtained from the Chandra 2 Msec survey and the Very Large Array, respectively. There is a good agreement between the X-ray, radio, and de-reddened UV estimates of the average SFR for our sample of z~2 galaxies of ~50 solar masses per year, indicating that the locally-calibrated SFR relations appear to be statistically valid from redshifts 1.5 < z < 3.0. We find that UV-estimated SFRs (uncorrected for extinction) underestimate the bolometric SFRs as determined from the 2-10 keV X-ray luminosity by a factor of ~4.5 to 5.0 for galaxies over a large range in redshift from 1.0 < z < 3.5.Comment: 5 pages, 1 figure, Accepted by ApJ Letter