Orientador: Prof. Dr. Jorge Tomioka / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Engenharia Elétrica, 2014. / No contexto energético, as mudanças climáticas e as crescentes crises energéticas aumentaram as preocupações e as pesquisas na área de acumuladores de energia, visando alcançar melhorias no cenário energético e ambiental global. Ao mesmo tempo, a sociedade tornou-se dependente do consumo de energia elétrica, sendo que falhas no fornecimento não são permitidas. Portanto, observa-se a necessidade da energia ofertada ser de boa qualidade e, principalmente, não sofrer interrupções. Atrelado a esses fatores, a bateria de Magnésio ¿ Ar passou a ser considerada uma fonte promissora de energia elétrica, principalmente pela abundância de Magnésio (sétimo elemento mais presente no planeta), por não poluir o meio ambiente, ser barata e possuir energia especifica elevada. Essas características transformam esse acumulador em um potencial substituto para outras tecnologias. No entanto, a bateria demagnésio possui desvantagens que precisam ser vencidas por meio de pesquisas para alavancar o seu uso comercial massivo. Sob essa perspectiva, neste trabalho propõe-se o estudo da liga de magnésio AZ91 para aplicação em baterias de Magnésio ¿ Ar, por meio de ensaios de porosidade e de dureza, como também análise microestrutural e mensuração do potencial de circuito aberto e das curvas de polarização potenciodinâmica, utilizando-se uma célula eletroquímica de três eletrodos e um potenciostato em diferentes tempos de imersão da liga AZ91 na solução eletrolítica de NaCl 0,1 M. A porosidade da peça, observada no microscópio óptico com ampliação de 50 vezes, revelou que em cada fase de solidificação existem poros de tamanhos diferentes, com distribuição específica. Conforme o processo de resfriamento ocorre, nota-se a presença de poros maiores. Relacionado à porosidade, a dureza apresentou valores maiores na fase inicial de solidificação, onde a porosidade é menor. Por meio da análise microestrutural, foi possível verificar a presença de dendritas, com uma complexa dispersão de segunda fase na liga (alumínio), porosidades e inclusões. As medidas de potencial de circuito aberto indicam uma tendência de resistência à corrosão em temposmaiores de contato da amostra com a solução de NaCl. Não foi possível observar passivação aparente na amostra, nem pontos de corrosão localizada (pite) nas curvas de polarização potenciodinâmica. As variações no potencial de corrosão apontaram uma maior resistência à corrosão em tempos de imersão maiores; contudo, os valores estáveis de densidade de corrente de corrosão demonstram que a velocidade de corrosão permaneceu constante, sendo que a camada de óxido formada não contribuiu na proteção do material. Para a aplicação em baterias de magnésio, esses resultados conferem uma limitação da liga AZ91, pois a camada de óxido formada pode prejudicar o funcionamento do dispositivo em processos de descarga intermitente. As principais formas de controlar a eficiência da bateria de Magnésio ¿ Ar são por meio da composição da liga, da oxigenação, do pH, da temperatura e da concentração de sais NaCl no eletrólito. / In the energy sector, weather changes and rising energy crisis raised concerns and research in energy accumulators to achieve improvements in overall environmental and energy scenario. At the same time, society has become dependent on electricity consumption, so failures in supply are not tolerated. Therefore, the energy needs to have a good quality, and not suffer interruptions. Coupled to these factors, the battery Magnesium ¿ Air has been considered a promising source of electricity, mainly by the abundance of magnesium (seventh-most element present on the planet), not to pollute the environment, be cheap and have high specific energy. These characteristics transform this accumulator in a potential substitute for other technologies. However, the magnesium battery has disadvantages that need to be overcome through research to leverage their massive commercial use. From this point of view, this study proposes the characterization of magnesium alloy AZ91 for application in batteries Magnesium ¿ Air, testing the porosity and hardness, as well as microstructural analysis, and the measurement of the open potential circuit and the potentiodynamic polarization, in various immersion times using an electrochemical cell with three electrodes. The porosity of the part, observed in the optical microscope, revealed that at each stage of solidification, the pores have different sizes and distribution. As the cooling process occurs, could observe the presence of larger pores. Associated to the porosity, hardness values were higher in the initial phase of solidification, where the porosity was less. Through microstructural analysis was verified the presence of dendrites, with a complex dispersion of second phase in the alloy (aluminum), porosity and inclusions. The open potential circuit indicated a tendency for corrosion resistance in greater immersion time in the solution of NaCl. In all cases, the potentiodynamic polarization curves did not exhibit apparent passivity, or points of localized corrosion (pitting). The changes in corrosion potential showed greater resistance to corrosion in immersion times larger, however, the steady state values of corrosion current density demonstrated that the corrosion rate remained constant and the oxide layer formed did not protect the material. For use in magnesium batteries, these results provided a limitation of the AZ91 alloy, because the oxide layer can disturb the functioning of the device in cases of intermittent discharge. The main ways to control the battery efficiency Magnesium ¿ Air are through the alloy composition, oxygenation, pH, temperature and salt concentration of NaCl in the electrolyte.

Global warming and depletion in fossil fuels have forced the society to search for alternate, clean sustainable energy sources. An obvious solution to the aforesaid problem lies in electrochemical energy storage systems like fuel cells and batteries. The desirable properties attributed to these devices like quick response, long life cycle, high round trip efficiency, clean source, low maintenance etc. have made them very attractive as energy storage devices. Compared to many advanced battery chemistries like nickel-metal hydride and lithium - ion batteries, metal-air batteries show several advantages like high energy density, ease of operation etc. The notable characteristics of metal - air batteries are the open structure with oxygen gas accessed from ambient air in the cathode compartment. These batteries rely on oxygen reduction and oxygen evolution reactions during discharging and charging processes. The efficiency of these systems is determined by the kinetics of oxygen reduction reaction. Platinum is the most preferred catalyst for many electrochemical reactions. However, high cost and stability issues restrict the use of Pt and hence there is quest for the development of stable, durable and active electrocatalysts for various redox reactions. The present thesis is directed towards exploring the electrocatalytic aspects of titanium carbonitride. TiCN, a fascinating material, possesses many favorable properties such as extreme hardness, high melting point, good thermal and electrical conductivity. Its metal-like conductivity and extreme corrosion resistance prompted us to use this material for various electrochemical studies. The work function as well as the bonding in the material can be tuned by varying the composition of carbon and nitrogen in the crystal lattice. The current study explores the versatility of TiCN as electrocatalyst in aqueous and non-aqueous media. One dimensional TiC0.7N0.3 nanowires are prepared by simple one step solvothermal method without use of any template and are characterized using various physicochemical techniques. The 1D nanostructures are of several µm size length and 40 ± 15 nm diameter (figure 1). Orientation followed by attachment of the primary particles results in the growth along a particular plane (figure 2). (a) (b) (c) Figure 1. (a) SEM images of TiC0.7N0.3 nanowires (b) TEM image and (c) High resolution TEM image showing the lattice fringes. (a) (b) (d) Figure 2. Bright field TEM images obtained at different time scales of reaction. (a) 0 h; (b) 12 h; (c) 72 h and (d) 144 h. The next aspect of the thesis discusses the electrochemical performance of TiC0.7N0.3 especially for oxygen reduction. Electrochemical oxygen reduction reaction (ORR) reveals that the nanowires possess high activity for ORR and involves four electron process leading to water as the product. The catalyst effectively converts oxygen to water with an efficiency of 85%. A comparison of the activity of different (C/N) compositions of TiCN is shown in figure 3. The composition TiC0.7N0.3 shows the maximum activity for the reaction. The catalyst is also very selective for ORR in presence of methanol and thus cross-over issue in fuel cells can be effectively addressed. Density functional theory (DFT) calculations also lead to the same composition as the best for electrocatalysis, supporting the experimental observations. Figure 3. Linear sweep voltammetric curves observed for different compositions of titanium carbonitride towards ORR. The next chapter deals with the use of TiC0.7N0.3 as air cathode for aqueous metal - air batteries. The batteries show remarkable performance in the gel- and in liquid- based electrolytes for zinc - air and magnesium - air batteries. A partial potassium salt of polyacrylic acid (PAAK) is used as the polymer to form a gel electrolyte. The cell is found to perform very well even at very high current densities in the gel electrolyte (figures 4 and 5). Figure 4 Photographs of different components of the gel - based zinc - air battery. (a) (b) Figure 5. a) Discharge curves at different current densities of 5, 20, 50 and 100 mA/cm2 for zinc-air system with TiC0.7N0.3 cathode b) Charge – discharge cycles at 50 mA/cm2 for the three electrode configuration with TiC0.7N0.3 nanowire for ORR and IrO2 for OER and Zn electrode (2h. cycle period). Similarly, the catalytic activity of TiC0.7N0.3 has also been explored in non-aqueous electrolyte. The material acts as a bifunctional catalyst for oxygen in non- aqueous medium as well. It shows a stable performance for more than 100 cycles with high reversibility for ORR and OER (figure 6). Li-O2 battery fabricated with a non-aqueous gel- based electrolyte yields very good output. (a) (b) (c) Figure 6. Galvanostatic charge –discharge cycles. (a) at 1 mA/cm2 (b) specific capacity as a function of no. of cycles (c) photographs of PAN-based gel polymer electrolyte. Another reaction of interest in non –aqueous medium is I-/I3-. redox couple. TiC0.7N0.3 nanowires show small peak to peak separation, low charge transfer resistance and hence high activity. The catalyst is used as a counter electrode in dye sensitized a solar cell that shows efficiencies similar to that of Pt, state of the art catalyst (figure 7). (a) (b) (c) Figure 7 (a) Cyclic voltammograms for I-/I3 - redox species on TiC0.7N0.3 nanowires (red), TiC0.7N0.3 particle (black) and Pt (blue). (b) Photocurrent density - voltage characteristics for DSSCs with different counter electrodes. TiC0.7N0.3 nanowire (black), TiC0.7N0.3 particle (blue), Pt (red). (c) Photograph of a sample cell. (a) (b) (c) (d) Figure 8 a) Comparison ORR activity for (i) NiTiO3(black), (ii) N-rGO (red), (iii) NiTiO3 – N-rGO (green) and (iv) Pt/C (blue) (b) Linear sweep voltammograms for OER observed on NiTiO3 – N-rGO composite (black), NiTiO3 (brown), N-rGO (blue), glassy carbon (red) in 0.5 M KOH. (c) Galvanostatic discharge curves of NiTiO3 – N-rGO as air electrode (d) Charge – discharge cycle at 5 mA/cm2 for the rechargeable battery with 10 min. cycle period. The last part of the thesis discusses about a ceramic oxide, nickel titanate. The electrocatalytic studies of the material towards ORR and OER reveal that the catalyst shows remarkable performance as a bifunctional electrode. A gel - based zinc - air battery fabricated with nickel titanate – reduced graphene oxide composite shows exceptional performance of 1000 charge-discharge cycles in the rechargeable mode (figure 8). Of course, the primary battery configuration works very well too The thesis contains seven chapters on the aspects mentioned above with summary and future perspectives given as the last chapter. An appendix based on TiN nanotubes and supercapacitor studies is given at the end.