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This thesis investigates several approaches to the development of high-performance batteries. A general background to the field and an introduction to the experimental methods used are given in Chapters 1 and 2 respectively. Chapter 3 presents a study of ordered and disordered LiNi₀.₅Mn₁.₅O₄ materials produced using an optimised resorcinol-formaldehyde gel (R-F gel) synthetic technique. Both materials exhibited good electrochemical properties and minimal side reaction with the electrolyte. Structural analyses of the materials in various states of discharge and charge were undertaken, and from these the charge / discharge processes were elucidated. In chapter 4 R-F gel synthesised Li(Ni₁/₃Mn₁/₃Co₁/₃)O₂ is studied and found to exhibit a high degree of structural stability on cycling, as well as excellent capacity, cyclability and rate capability. Photoelectron spectroscopy studies revealed that the R-F gel derived particles have highly stable surfaces. A discussion of the results and their significance, with particular regard to the outstanding electrochemical performance observed, is also presented. Chapter 5 sets out an investigation into the nature of R-F gel synthesised 0.5Li₂MnO₃:0.5LiNi₁/₃Mn₁/₃Co₁/₃O₂. The electrochemical data revealed that, after an initial activation stage, the R-F gel derived material exhibited a high capacity, good cyclability and exceptional rate capability. This chapter also considers some initial structural investigations and the electrochemical processes occurring on charge. In chapter 6 the use of ether-based electrolytes, combined with various cathode materials, in lithium-oxygen batteries is examined. The formation of decomposition products was observed, and a scheme suggesting probable reaction pathways is given. It was noted that significant quantities of the desired discharge product, lithium peroxide, were formed on the 1st cycle discharge, implying some electrolyte / cathode combinations do demonstrate a degree of stability. A summary of the results and a discussion of their significance are also included.

Submitted by Daniele Amaral (daniee_ni@hotmail.com) on 2016-09-23T19:09:03Z No. of bitstreams: 1 DissYBC.pdf: 3413811 bytes, checksum: 15a1d9802b831630809df811dba9948a (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-26T18:34:50Z (GMT) No. of bitstreams: 1 DissYBC.pdf: 3413811 bytes, checksum: 15a1d9802b831630809df811dba9948a (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-09-26T18:34:57Z (GMT) No. of bitstreams: 1 DissYBC.pdf: 3413811 bytes, checksum: 15a1d9802b831630809df811dba9948a (MD5) / Made available in DSpace on 2016-09-26T18:35:04Z (GMT). No. of bitstreams: 1 DissYBC.pdf: 3413811 bytes, checksum: 15a1d9802b831630809df811dba9948a (MD5) Previous issue date: 2014-07-02 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / The growing number of cyclists pedaling in Brazilian cities demand an effort of local governments to develop actions to make their cities more bicycle friendly. However, these actions have been carried out without a plan that ensures the necessary priority to bicycle mobility. Thus, this study sought to evaluate how much the Brazilian cities are bicycle friendly, its cyclability. The relief, climate, urban aspects, pollution, integration of cycling with public transport, the quality of roads, safety, cycling infrastructure and government actions of Brazilian cities were evaluated through an online questionnaire answered by 2,925 people throughout Brazil. The survey results presented in this work show a good picture of the current situation of cyclability in Brazil: lack quality of infrastructure, lack of comfortable roads, lack of security and lack of government commitment to bicycle mobility to change this reality. / O crescente número de ciclistas pedalando nas cidades brasileiras demanda um esforço dos governos locais para desenvolver ações em busca de tornar as cidades mais amigas da bicicleta. Porém, estas ações vêm sendo realizadas sem um planejamento que garanta a prioridade necessária à mobilidade por bicicleta. Com isso, esta pesquisa buscou avaliar o quanto as cidades brasileiras são amigas da bicicleta, a Ciclabilidade. O relevo, o clima, aspectos urbanos, a poluição, a integração da bicicleta com o transporte público, a qualidade das vias, a segurança, a infraestrutura cicloviária e as ações governamentais das cidades brasileiras foram avaliadas através de um questionário online respondido por 2925 pessoas de todo o Brasil. Os resultados da pesquisa apresentados nesta dissertação mostram um quadro nada bom da situação atual da Ciclabilidade no Brasil. Falta infraestrutura de qualidade, vias confortáveis, segurança e comprometimento do governo com a bicicleta para alterar esta realidade.

In dieser Arbeit werden kompaktierte Verbundwerkstoffe aus verschiedenen Speichermaterialien mit expandiertem Naturgraphit (ENG) in Hinblick auf die Anwendung als dynamische Wasserstofffeststoffspeichermaterialien untersucht. Pulverförmige hydridbildende Ausgangsmaterialien wurden mit bis zu 25 Masse-% ENG vermischt und bei Pressdrücken bis 600 MPa kompaktiert. Um einen weiten Anwendungsbereich abzudecken wurden ein Niedrigtemperaturmaterial (Ti-Mn-basierte Legierung; 0°C bis 100°C), zwei Mitteltemperaturmaterialien (Amid- und Alanatsystem; 100°C bis 200°C) und ein Hochtemperaturmaterial (Magnesium-Nickel-Legierung; 250°C bis 400°C) basierend auf einer umfangreichen Literaturrecherche gewählt. Die Verbundwerkstoffe weisen eine erhöhte radiale Wärmeleitfähigkeit auf und zeichnen sich im Vergleich zu herkömmlich verwendeten Pulverschüttungen durch höhere volumetrische Wasserstoffspeicherdichten aus. Im Fokus der Untersuchungen stehen vor allem die im Hinblick auf Anwendungstauglichkeit wesentlichen Eigenschaften der Verbundwerkstoffe. So wurde z.B. der Wasserstoffdruck während der Dehydrierung variiert, um sicher zu stellen, Verbraucher mit üblichen Überdrücken versorgen zu können. Darüber hinaus wurde die Stabilität, Gaspermeabilität, Wärmeleitfähigkeit und Porosität der Presslinge im Verlauf zyklischer Hydrierung evaluiert und diskutiert. Insgesamt zeichnet sich ein hohes Potenzial ab, derartige Presslinge als Wasserstoffspeichermaterial für verschiedene Anwendungen entsprechend der jeweiligen Arbeitstemperaturen und weiteren Randbedingungen (z.B. Systemmasse, Tankvolumen etc.) zu verwenden. Diesbezüglich konnte mittels eines Tankdemonstrators basierend auf dem Ti-Mn-System ein Wasserstofffahrzeug erfolgreich betrieben und somit auch die Praxistauglichkeit der Hydrid-Graphit-Verbundmaterialien gezeigt werden. / Compacted composites of solid-state hydrogen storage materials and expanded natural graphite (ENG) are investigated in view of their potential for hydrogen storage applications. Powdery hydride-forming materials were blended with up to 25 weight-% ENG and compacted with up to 600 MPa compaction pressure. In order to cover a wide range of possible applications one low-temperature material (Ti-Mn-based alloy; 0°C to 100°C), two mid-temperature materials (amide and alante system; 100°C to 200°C) and one high-temperature material (magnesium-nickel alloy; 250°C to 400°C) were chosen based on a thorough literature review. The composites result in an increased radial thermal conductivity and are superior in their volumetric hydrogen storage density compared to commonly used loose powder beds. The research is focused on the applicability of suchlike prepared composites. In this regard, the dehydrogenation back-pressures were varied to ensure a sufficient supply pressure of common consumer loads. Furthermore, the stability, gas permeability, thermal conductivity and porosity throughout cyclic hydrogenation were evaluated and discussed. Overall, a high potential to use suchlike composite materials for hydrogen storage applications regarding the specific working conditions (temperature, system mass, available volume etc.) is found. In this regard, a demonstrator tank equipped with Ti-Mn-based system was successfully supplying a hydrogen driven vehicle, which proves the feasibility of these hydride-graphite composite materials.

In dieser Arbeit werden kompaktierte Verbundwerkstoffe aus verschiedenen Speichermaterialien mit expandiertem Naturgraphit (ENG) in Hinblick auf die Anwendung als dynamische Wasserstofffeststoffspeichermaterialien untersucht. Pulverförmige hydridbildende Ausgangsmaterialien wurden mit bis zu 25 Masse-% ENG vermischt und bei Pressdrücken bis 600 MPa kompaktiert. Um einen weiten Anwendungsbereich abzudecken wurden ein Niedrigtemperaturmaterial (Ti-Mn-basierte Legierung; 0°C bis 100°C), zwei Mitteltemperaturmaterialien (Amid- und Alanatsystem; 100°C bis 200°C) und ein Hochtemperaturmaterial (Magnesium-Nickel-Legierung; 250°C bis 400°C) basierend auf einer umfangreichen Literaturrecherche gewählt. Die Verbundwerkstoffe weisen eine erhöhte radiale Wärmeleitfähigkeit auf und zeichnen sich im Vergleich zu herkömmlich verwendeten Pulverschüttungen durch höhere volumetrische Wasserstoffspeicherdichten aus. Im Fokus der Untersuchungen stehen vor allem die im Hinblick auf Anwendungstauglichkeit wesentlichen Eigenschaften der Verbundwerkstoffe. So wurde z.B. der Wasserstoffdruck während der Dehydrierung variiert, um sicher zu stellen, Verbraucher mit üblichen Überdrücken versorgen zu können. Darüber hinaus wurde die Stabilität, Gaspermeabilität, Wärmeleitfähigkeit und Porosität der Presslinge im Verlauf zyklischer Hydrierung evaluiert und diskutiert. Insgesamt zeichnet sich ein hohes Potenzial ab, derartige Presslinge als Wasserstoffspeichermaterial für verschiedene Anwendungen entsprechend der jeweiligen Arbeitstemperaturen und weiteren Randbedingungen (z.B. Systemmasse, Tankvolumen etc.) zu verwenden. Diesbezüglich konnte mittels eines Tankdemonstrators basierend auf dem Ti-Mn-System ein Wasserstofffahrzeug erfolgreich betrieben und somit auch die Praxistauglichkeit der Hydrid-Graphit-Verbundmaterialien gezeigt werden. / Compacted composites of solid-state hydrogen storage materials and expanded natural graphite (ENG) are investigated in view of their potential for hydrogen storage applications. Powdery hydride-forming materials were blended with up to 25 weight-% ENG and compacted with up to 600 MPa compaction pressure. In order to cover a wide range of possible applications one low-temperature material (Ti-Mn-based alloy; 0°C to 100°C), two mid-temperature materials (amide and alante system; 100°C to 200°C) and one high-temperature material (magnesium-nickel alloy; 250°C to 400°C) were chosen based on a thorough literature review. The composites result in an increased radial thermal conductivity and are superior in their volumetric hydrogen storage density compared to commonly used loose powder beds. The research is focused on the applicability of suchlike prepared composites. In this regard, the dehydrogenation back-pressures were varied to ensure a sufficient supply pressure of common consumer loads. Furthermore, the stability, gas permeability, thermal conductivity and porosity throughout cyclic hydrogenation were evaluated and discussed. Overall, a high potential to use suchlike composite materials for hydrogen storage applications regarding the specific working conditions (temperature, system mass, available volume etc.) is found. In this regard, a demonstrator tank equipped with Ti-Mn-based system was successfully supplying a hydrogen driven vehicle, which proves the feasibility of these hydride-graphite composite materials.

This doctoral thesis deals with synthesis and characterisation of electroactive electrode materials for li-ion batteries and accumulators. The work is divided into two main parts. One deals with LiFePO4 based cathode composite electroactive material and in the second is described the synthesis and utilization of monoclinic TiO2(B) as an anode for li-ion cell. The main aim of the work is to relate the synthesis procedure and structural properties of both materials to its electrochemical preformance.

The transition from fossil fuels to renewable resources has created more demand for energy storage devices. Lithium-oxygen (Li-O2) batteries have attracted much attention due to their high theoretical energy densities. They, however, are still in their infancy and several fundamental challenges remain to be addressed. Advanced analytical techniques have revealed that all components of a Li-O2 battery undergo undesirable degradation during discharge/charge cycling, contributing to reduced cyclability. Despite many attempts to minimize the anode and cathode degradation, the electrolyte remains as the leading cause for rapid capacity fading and poor cyclability in Li-O2 batteries. In this dissertation, composite gel polymer electrolytes (cGPEs) consisting of a UV-curable polymer, tetragylme based electrolyte, and glass microfibers with a diameter of ~1 µm and an aspect ratio of >100 have been developed for their use in Li-O2 battery application. The Li-O2 batteries containing cGPEs showed superior charge/discharge cycling for 500 mAh.g-1 cycle capacity with as high as 400% increase in cycles for cGPE over gel polymer electrolytes (GPEs). Results using in-situ electrochemical impedance spectroscopy (EIS), Raman spectroscopy, and scanning electron microscopy revealed that the source of the improvement was the reduction of the rate of lithium carbonates formation on the surface of the cathode. This decrease in formation rate afforded by cGPE-containing batteries was possible due to the decrease of the rate of electrolyte decomposition. The increase in solvated to the paired Li+ ratio at the cathode, afforded by increased lithium transference number, helped lessen the probability of superoxide radicals reacting with the tetraglyme solvent. This stabilization during cycling helped prolong the cycling life of the batteries. The effect of ion complexes on the stability of liquid glyme based electrolytes with various lithium salt concentrations has also been investigated for Li-O2 batteries. Charge/discharge cycling with a cycle capacity of 500 mAh·g-1 showed an improvement as high as 300% for electrolytes containing higher lithium salt concentrations. Analysis of the Raman spectroscopy data of the electrolytes suggested that the increase in lithium salt concentration afforded the formation of cation-solvent complexes, which in turn, mitigated the tetragylme degradation.