Novel Synthetic Routes to Carbon Composite Electrochemical Materials

Reduced graphene oxide (rGO) has been regarded as a major step in the advancement of graphene’s implementation into electrochemical storage mechanisms. The issue that has arisen is that by improving one beneficial characteristic, it will be detrimental for another (i.e., conductivity and surface area). The creation of polymer or nanoparticular based rGO composites allows for these issues to be navigated and potentially avoided with its correct non-damaging implementation. This thesis explores the fundamental shaping and functionalisation of reduced graphene based, before investigating the benefits and detriments to utilising the use of assistive mechanics of long chained polyanilines, tethered amino alcohol silver nanoparticles and aluminium interlayer insertions. All of these materials are monitored with an array of physical characterisation techniques to better understand the composition and the mechanical mechanisms of the undertaken electrochemical reactions. A reduced graphene oxide behaves as an appropriate base in which to deposit polyaniline, so to increase the conductivity in an attempt to prevent compromising the specific surface area and therefore improve the charge storage mechanism. This leads into interlayer aluminium metal insertion which presents a greater focus towards improving the electrolytic interaction between electrode and electrolyte by improving ion accessibility and porosity. In demonstrating rGO’s diversity, the oxygen reduction reaction can be undertaken as part of an anion exchange membrane fuel cell, studying the effects of using alternative precursors and deposition techniques in order to bind silver nanoparticles to the surface of the functionalised graphene. This exhibited preliminary results demonstrating an onset potential 70 mV more positive than the current Ag/C commercial model. The materials introduced throughout the study provide the groundwork for the improvements of supercapacitors and ORR catalysis, but also create opportunities for these composites and techniques to be used for alternative non-electrochemical research

Exploring anodes for calcium-ion batteries

Calcium ion batteries have been increasingly explored as an alternative energy storage system as industry begins to manoeuvre towards an age of ‘Beyond lithium-ion’ research and development. However, using calcium metal as the battery's anode presents a multitude of issues, including the inability to strip ions off the metal, and the creation of an inactive passivation layer. Most research conducted around calcium ion batteries focuses on the electrolytic and cathodic study, whereas little focuses on the anode, due in part to the complexity and difficulty in resolving its challenges. Herein, this review will address the issues calcium has, including its lack of reversibility and solid electrolyte interface formation, as well as explore the alternative anode materials that have been utilised, noting their viability and future prospects

Cosmological Constraints from Galaxy Clustering and the Mass-to-Number Ratio of Galaxy Clusters

We place constraints on the average density (Omega_m) and clustering amplitude (sigma_8) of matter using a combination of two measurements from the Sloan Digital Sky Survey: the galaxy two-point correlation function, w_p, and the mass-to-galaxy-number ratio within galaxy clusters, M/N, analogous to cluster M/L ratios. Our w_p measurements are obtained from DR7 while the sample of clusters is the maxBCG sample, with cluster masses derived from weak gravitational lensing. We construct non-linear galaxy bias models using the Halo Occupation Distribution (HOD) to fit both w_p and M/N for different cosmological parameters. HOD models that match the same two-point clustering predict different numbers of galaxies in massive halos when Omega_m or sigma_8 is varied, thereby breaking the degeneracy between cosmology and bias. We demonstrate that this technique yields constraints that are consistent and competitive with current results from cluster abundance studies, even though this technique does not use abundance information. Using w_p and M/N alone, we find Omega_m^0.5*sigma_8=0.465+/-0.026, with individual constraints of Omega_m=0.29+/-0.03 and sigma_8=0.85+/-0.06. Combined with current CMB data, these constraints are Omega_m=0.290+/-0.016 and sigma_8=0.826+/-0.020. All errors are 1-sigma. The systematic uncertainties that the M/N technique are most sensitive to are the amplitude of the bias function of dark matter halos and the possibility of redshift evolution between the SDSS Main sample and the maxBCG sample. Our derived constraints are insensitive to the current level of uncertainties in the halo mass function and in the mass-richness relation of clusters and its scatter, making the M/N technique complementary to cluster abundances as a method for constraining cosmology with future galaxy surveys.Comment: 23 pages, submitted to Ap

Interphases in the electrodes of potassium ion batteries

Rechargeable potassium-ion batteries (PIBs) are of great interest as a sustainable, environmentally friendly, and cost-effective energy storage technology. The electrochemical performance of a PIB is closely related to the reaction kinetics of active materials, ionic/electronic transport, and the structural/electrochemical stability of cell components. Alongside the great effort devoted in discovering and optimising electrode materials, recent research unambiguously demonstrates the decisive role of the interphases that interconnect adjacent components in a PIB. Knowledge of interphases is currently less comprehensive and satisfactory compared to that of electrode materials, and therefore, understanding the interphases is crucial to facilitating electrode materials design and advancing battery performance. The present review aims to summarise the critical interphases that dominate the overall battery performance of PIBs, which includes solid-electrolyte interphase, cathode-electrolyte interphase, and solid–solid interphases within composite electrodes, via exploring their formation principles, chemical compositions, and determination of reaction kinetics. State-of-the-art design strategies of robust interphases are discussed and analysed. Finally, perspectives are given to stimulate new ideas and open questions to further the understanding of interphases and the development of PIBs

Weak Lensing Peak Finding: Estimators, Filters, and Biases

Large catalogs of shear-selected peaks have recently become a reality. In order to properly interpret the abundance and properties of these peaks, it is necessary to take into account the effects of the clustering of source galaxies, among themselves and with the lens. In addition, the preferred selection of lensed galaxies in a flux- and size-limited sample leads to fluctuations in the apparent source density which correlate with the lensing field (lensing bias). In this paper, we investigate these issues for two different choices of shear estimators which are commonly in use today: globally-normalized and locally-normalized estimators. While in principle equivalent, in practice these estimators respond differently to systematic effects such as lensing bias and cluster member dilution. Furthermore, we find that which estimator is statistically superior depends on the specific shape of the filter employed for peak finding; suboptimal choices of the estimator+filter combination can result in a suppression of the number of high peaks by orders of magnitude. Lensing bias generally acts to increase the signal-to-noise \nu of shear peaks; for high peaks the boost can be as large as \Delta \nu ~ 1-2. Due to the steepness of the peak abundance function, these boosts can result in a significant increase in the abundance of shear peaks. A companion paper (Rozo et al., 2010) investigates these same issues within the context of stacked weak lensing mass estimates.Comment: 11 pages, 8 figures; comments welcom

The microbiome of pest insects:It is not just bacteria

Insects are associated with multiple microbes that have been reported to influence various aspects of their biology. Most studies in insects, including pest species, focus on the bacterial communities of the microbiome even though the microbiome consists of members of many more kingdoms, which can also have large influence on the life history of insects. In this review, we present some key examples of how the different members of the microbiome, such as bacteria, fungi, viruses, archaea, and protozoa, affect the fitness and behavior of pest insects. Moreover, we argue that interactions within and among microbial groups are abundant and of great importance, necessitating the use of a community approach to study microbial-host interactions. We propose that the restricted focus on bacteria very likely hampers our understanding of the functioning and impact of the microbiome on the biology of pest insects. We close our review by highlighting a few open questions that can provide an in-depth understanding of how other components of the microbiome, in addition to bacteria, might influence host performance, thus contributing to pest insect ecology

Estimating Luminosity Function Constraints from High-Redshift Galaxy Surveys

The installation of the Wide Field Camera 3 (WFC3) on the Hubble Space Telescope (HST) will revolutionize the study of high-redshift galaxy populations. Initial observations of the HST Ultra Deep Field (UDF) have yielded multiple z>~7 dropout candidates. Supplemented by the Great Observatory Origins Deep Survey (GOODS) Early Release Science (ERS) and further UDF pointings, these data will provide crucial information about the most distant known galaxies. However, achieving tight constraints on the z~7 galaxy luminosity function (LF) will require even more ambitious photometric surveys. Using a Fisher matrix approach to fully account for Poisson and cosmic sample variance, as well as covariances in the data, we estimate the uncertainties on LF parameters achieved by surveys of a given area and depth. Applying this method to WFC3 z~7 dropout galaxy samples, we forecast the LF parameter uncertainties for a variety of model surveys. We demonstrate that performing a wide area (~1 deg^2) survey to H_AB~27 depth or increasing the UDF depth to H_AB~30 provides excellent constraints on the high-z LF when combined with the existing UDF GO and GOODS ERS data. We also show that the shape of the matter power spectrum may limit the possible gain of splitting wide area (>~0.5 deg^2) high-redshift surveys into multiple fields to probe statistically independent regions; the increased root-mean-squared density fluctuations in smaller volumes mostly offset the improved variance gained from independent samples.Comment: Version accepted by ApJ

Annealing a Follow-up Program: Improvement of the Dark Energy Figure of Merit for Optical Galaxy Cluster Surveys

The precision of cosmological parameters derived from galaxy cluster surveys is limited by uncertainty in relating observable signals to cluster mass. We demonstrate that a small mass-calibration follow-up program can significantly reduce this uncertainty and improve parameter constraints, particularly when the follow-up targets are judiciously chosen. To this end, we apply a simulated annealing algorithm to maximize the dark energy information at fixed observational cost, and find that optimal follow-up strategies can reduce the observational cost required to achieve a specified precision by up to an order of magnitude. Considering clusters selected from optical imaging in the Dark Energy Survey, we find that approximately 200 low-redshift X-ray clusters or massive Sunyaev-Zel'dovich clusters can improve the dark energy figure of merit by 50%, provided that the follow-up mass measurements involve no systematic error. In practice, the actual improvement depends on (1) the uncertainty in the systematic error in follow-up mass measurements, which needs to be controlled at the 5% level to avoid severe degradation of the results; and (2) the scatter in the optical richness-mass distribution, which needs to be made as tight as possible to improve the efficacy of follow-up observations.Comment: 12 pages, 7 figures, replaced to match published versio

The X-ray Cluster Normalization of the Matter Power Spectrum

The number density of galaxy clusters provides tight statistical constraints on the matter fluctuation power spectrum normalization, traditionally phrased in terms of sigma_8, the root mean square mass fluctuation in spheres with radius 8 h^-1 Mpc. We present constraints on sigma_8 and the total matter density Omega_m0 from local cluster counts as a function of X-ray temperature, taking care to incorporate and minimize systematic errors that plagued previous work with this method. In particular, we present new determinations of the cluster luminosity - temperature and mass - temperature relations, including their intrinsic scatter, and a determination of the Jenkins mass function parameters for the same mass definition as the mass - temperature calibration. Marginalizing over the 12 uninteresting parameters associated with this method, we find that the local cluster temperature function implies sigma_8 (Omega_m0/0.32)^alpha = 0.86+/-0.04 with alpha = 0.30 (0.41) for Omega_m0 < 0.32 (Omega_mo > 0.32) (68% confidence for two parameters). This result agrees with a wide range of recent independent determinations, and we find no evidence of any additional sources of systematic error for the X-ray cluster temperature function determination of the matter power spectrum normalization. The joint WMAP5 + cluster constraints are: Omega_m0 = 0.30+0.03/-0.02 and sigma_8 = 0.85+0.04/-0.02 (68% confidence for two parameters).Comment: 31 pages, 16 figures, accept for publication in ApJ 609, Jan. 10, 200

Enabling intercalation-type TiNb24O62 anode for sodium- and potassium-ion batteries via a synergetic strategy of oxygen vacancy and carbon incorporation

The key to develop earth-abundant energy storage technologies sodium- and potassium-ion batteries (SIBs and PIBs) is to identify low-cost electrode materials that allow fast and reversible Na+/K+ intercalation. Here, we report an intercalation-type material TiNb24O62 as a versatile anode for SIBs and PIBs, via a synergistic strategy of oxygen vacancy and carbon incorporation to enhance ion and electron diffusion. The TiNb24O62−x/reduced graphene oxide (rGO) composite anode delivers high reversible capacities (130 mA h g−1 for SIBs and 178 mA h g−1 for PIBs), great rate performance (54 mA h g−1 for SIBs and 37 mA h g−1 for PIBs at 1 A g−1), and superior cycle stability (73.7% after 500 cycles for SIBs and 84% after 300 cycles for PIBs). The performance is among the best results of intercalation-type metal oxide anodes for SIBs and PIBs. The better performance of TiNb24O62−x/rGO in SIBs than PIBs is due to the better reaction kinetics of the former. Moreover, mechanistic study confirms that the redox activity of Nb4+/5+ is responsible for the reversible intercalation of Na+/K+. Our results suggest that TiNb24O62−x/rGO is a promising anode for SIBs and PIBs and may stimulate further research on intercalation-type compounds as candidate anodes for large ion batteries