Biomass-derived carbon materials for energy storage applications

Energy storage systems are an essential link in the implementation of renewable energies and in the development of electric vehicles, which are needed to reduce our dependence on fossil fuels and the emission of greenhouse gases. Various technologies have been proposed for energy storage based on different working principles, including lithium-ion batteries, emerging sodium-ion batteries and electric-double layer capacitors. Besides the quest for improving key aspects such as energy and power densities, current research efforts are devoted to foster the manufacturing of more environmentally friendly devices using sustainable materials. Carbon-based electrodes hold considerable promise in such terms due to their low cost, tailorable morphology and microstructure, and the possibility of processing them by direct carbonization of eco-friendly and naturally-available biomass resources. The main goal of this thesis is to develop carbon materials from biomass resources and study their applications as electrode for lithium-ion batteries, sodium-ion batteries and electric-double layer capacitors. En route towards that goal, it also aims at expanding our understanding of the microstructural changes of biomass-derived carbons with varying processing conditions and their effect on the electrochemical performance for each of these technologies. The first part of this work reports on the synthesis of graphitized carbon materials from biomass resources by means of an Fe catalyst, and the study of their electrochemical performance as anode materials for lithium-ion batteries (LIBs). Peak carbonization temperatures between 850 °C and 2000 ºC were covered to study the effect of crystallinity, surface and microstructural parameters on the anodic behavior, focusing on the first-cycle Coulombic efficiency, reversible specific capacity and rate performance. Reversible capacities of Fe-catalyzed biomass-derived carbons were compared to non-catalyzed hard carbon and soft carbons materials heated up to 2800 ºC. Moreover, in-situ characterization experiments were carried out to advance our understanding of the mechanisms responsible for catalytic graphitization. The second part of this work reports a comprehensive study on the structural evolution of hard carbons from biomass resources as a function of carbonization temperature (800 - 2000 ºC), and its correlation with electrochemical properties as anode materials for sodium-ion batteries (SIBs). Synchrotron X-ray total scattering experiments were performed and the associated atomic pair distribution function (PDF) extracted from the data to access quantitative information on local atomic arrangement in these amorphous materials at the nanoscale, as well as its evolution with increasing processing temperature. Then, electrochemical properties and the storage mechanisms involved on Na ions insertion into hard carbon structures at each characteristic potential regions were elucidated and correlated with microstructural properties. Finally, the third part of this work reports on the synthesis of nanostructured porous graphene-like materials from biomass resources using an explosion-assisted activation strategy by nitrate compounds and Ni as a graphitization catalyst. The thermal behavior during carbonization as well as the resulting microstructural and surface properties were evaluated at two different processing temperatures, 300 and 1000 ºC. Finally, their application as electrode materials for electric-double layer capacitors (EDLCs) and LIBs is investigated, with a view to their performance under high charge/discharge specific current densities experiments.Premio Extraordinario de Doctorado U

Magnetic susceptibility of glassy carbon

Magnetic susceptibility of glassy carbon at room temperature with respect to magnetic field strength, heat treatment temperature, and high temperature tensile deformatio

Imaging the atomic structure of activated carbon

The precise atomic structure of activated carbon is unknown, despite its huge commercial importance in the purification of air and water. Diffraction methods have been extensively applied to the study of microporous carbons, but cannot provide an unequivocal identification of their structure. Here we show that the structure of a commercial activated carbon can be imaged directly using aberration-corrected transmission electron microscopy. Images are presented both of the as-produced carbon and of the carbon following heat treatment at 2000 degrees C. In the 2000 degrees C carbon clear evidence is found for the presence of pentagonal rings, suggesting that the carbons have a fullerene-related structure. Such a structure would help to explain the properties of activated carbon, and would also have important implications for the modelling of adsorption on microporous carbons

Simulating the Initial Stage of Phenolic Resin Carbonization via the ReaxFF Reactive Force Field

Pyrolysis of phenolic resins leads to carbon formation. Simulating this resin-to-carbon process atomistically is a daunting task. In this paper, we attempt to model the initial stage of this process by using the ReaxFF reactive force field, which bridges quantum mechanical and molecular mechanical methods. We run molecular dynamics simulations to examine the evolution of small molecules at different temperatures. The main small-molecule products found include H_2O, H_2, CO, and C_2H_2. We find multiple pathways leading to H_2O formation, including a frequent channel via β-H elimination, which has not been proposed before. We determine the reaction barrier for H_2O formation from the reaction rates obtained at different temperatures. We also discuss the relevance of our simulations to previous experimental observations. This work represents a first attempt to model the resin-to-carbon process atomistically

Electric utility acid fuel cell stack technology advancement

The principal effort under this program was directed at the fuel cell stack technology required to accomplish the initial feasibility demonstrations of increased cell stack operating pressures and temperatures, increased cell active area, incorporation of the ribbed substrate cell configuration at the bove conditions, and the introduction of higher performance electrocatalysts. The program results were successful with the primary accomplishments being: (1) fabrication of 10 sq ft ribbed substrate, cell components including higher performing electrocatalysts; (2) assembly of a 10 sq ft, 30-cell short stack; and (3) initial test of this stack at 120 psia and 405 F. These accomplishments demonstrate the feasibility of fabricating and handling large area cells using materials and processes that are oriented to low cost manufacture. An additional accomplishment under the program was the testing of two 3.7 sq ft short stacks at 12 psia/405 F to 5400 and 4500 hours respectively. These tests demonstrate the durability of the components and the cell stack configuration to a nominal 5000 hours at the higher pressure and temperature condition planned for the next electric utility power plant

Structure dependence of the diamagnetism of graphitizing carbons

Structure dependence of diamagnetism in pyrolytic carbon

Fullerene-like models for microporous carbon: a review

Microporous carbons are important in a wide variety of applications, ranging from pollution control to supercapacitors, yet their structure at the molecular level is poorly understood. Over the years, many structural models have been put forward, but none have been entirely satisfactory in explaining the properties of the carbons. The discovery of fullerenes and fullerene-related structures such as carbon nanotubes gave us a new perspective on the structure of solid carbon, and in 1997 it was suggested that microporous carbon may have a structure related to that of the fullerenes. Recently, evidence in support of such a structure has been obtained using aberration-corrected transmission electron microscopy, electron energy loss spectroscopy and other techniques. This article describes the development of ideas about the structure of microporous carbon, and reviews the experimental evidence for a fullerene-related structure. Theoretical models of the structural evolution of microporous carbon are summarised, and the use of fullerene-like models to predict the adsorptive properties of microporous carbons are reviewed

Microsegregation in Nodular Cast Iron with Carbides

In this paper results of microsegregation in the newly developed nodular cast iron with carbides are presented. To investigate the pearlitic and bainitic cast iron with carbides obtained by Inmold method were chosen. The distribution of linear elements on the eutectic cell radius was examined. To investigate the microsegregation pearlitic and bainitic cast iron with carbides obtained by Inmold method were chosen.The linear distribution of elements on the eutectic cell radius was examined. Testing of the chemical composition of cast iron metal matrix components, including carbides were carried out. The change of graphitizing and anti-graphitizing element concentrations within eutectic cell was determined. It was found, that in cast iron containing Mo carbides crystallizing after austenite + graphite eutectic are Si enriched

Carbons produced from known organic compounds 2. Anthracene-biphenyl and phenanthrene- biphenyl systems

Carbonization of binary mixtures of anthracene biphenyl and penanthrene bipheny