A test cryostat was constructed to investigate the potential of a locally made thermal battery. A thermal battery is proposed to be a useful component in the construction of future superconducting fault current limiter (SFCL) systems. The heat generated from a SFCL under quench conditions can be conducted into a solid nitrogen thermal battery. This is an alternative to using a liquid cryogen which on evaporation would form a highly nonconductive vapour layer around the SFCL and could be potentially explosive. The relevant heat transfer mechanisms for cryostat design were analyzed to ensure that the cryostat was capable of solidifying nitrogen and thus be used as a thermal battery. The experimental stage was ultimately capable of reaching a temperature of 40 K. Using a resistor to mimic the normal state of a superconductor, the performance of the thermal battery was determined by subjecting it to transient thermal events. The effect of solid nitrogen crystal size was investigated by performing pulse tests on solid nitrogen formed at different rates. It was found that slowly formed solid nitrogen performed better and stabilised the resistor’s temperature more quickly. The phenomenon of ‘dry-out’ was also investigated for different formation rates by subjecting the solid nitrogen to multiple heating pulses. It was found to become very significant after the first pulse when using quickly formed solid nitrogen, but did not manifest in slowly formed solid nitrogen. / Thesis (M.Sc.Eng.)-University of KwaZulu-Natal, Durban, 2011.

[pt] Neste trabalho é realizada a determinação dos parâmetros cinéticos críticos da redução eletroquímica do dissulfeto de ferro numa mistura de haletos clorados fundidos. Este catodo é empregado como material alternativo em sistemas de elevado grau tecnológico, por exemplo, componente em coletores de energia solar, anodo despolarizador para a produção de hidrogênio e material catódico em baterias e pilhas de alta densidade de energia. Cabe ressaltar que o par eletroquímico Li / FeS2 vem sendo testado em novas configurações com diversos eletrólitos, especialmente com sais fundidos em pilhas térmicas e polímeros orgânicos em veículos elétricos / híbridos. Os ensaios desta pesquisa foram realizados em uma célula de teste num forno vertical com leitura digital em tempo real da temperatura e dos dados eletroquímicos. A estabilidade de diversos eletrodos de referência de primeira espécie foi avaliada em testes em branco de longa duração, sendo analisados os seguintes materiais: prata, platina, níquel, molibdênio. A célula eletroquímica teve a configuração de três eletrodos: prata como referência; dissulfeto de ferro, na forma de pó compactado, de trabalho e grafite sendo o contra-eletrodo. A metodologia empregada foi a voltametria linear cíclica com taxa de varredura lenta (0,002 Vs-1), garantindo quasi equilíbrio. O cálculo dos potenciais padrão em circuito aberto, de equilíbrio termodinâmico, indicou 0,3306 ± 0,014 V (773 K) em relação ao eletrodo de referência de Ag / AgCl. O coeficiente de transferência catódico ficou determinado como valendo 0,48, comprovando a reversibilidade do processo e apontando para a possibilidade de utilização deste sistema eletroquímico em baterias. Foi estudado o comportamento eletrocatalítico do eletrodo de FeS2 pelo levantamento das curvas de Tafel a partir dos voltamogramas. O parâmetro indicador desta espontaneidade reacional foi as correntes de transferência, que para o sistema foram determinadas como 14,75 ± 2,73 kA m-2. A avaliação dos produtos reacionais e intermediários foi realizada aliando dados eletroquímicos e técnicas de caracterização. O mecanismo de reação proposto é iniciado pela redução do FeS2 a Fe metálico, como etapa controladora da reação, envolvendo a troca de um elétron, seguida de duas reações envolvendo íons enxofre e uma etapa final puramente química com a formação de Li2S. Uma série de reações químicas e eletroquímicas são propostas para explicar a formação de polissulfetos intermediários, sendo o mais importante o Li2FeS2 ( fase X ), caracterizado neste estudo através de micrografias com a formação de cristais de hábito acicular. / [en] In this work the measurement of the critical kinetics parameters of iron disulphide electrochemical reduction in molten chloride halides mixture was made. This cathode is applied as alternative material in high technology systems, such as, solar energy collector`s components, anode depolariser for hydrogen production and cathodic materials for high energy density primary and secondary batteries. It should be notice that the Li / FeS2 electrochemical pair is being tested in new configurations together with several electrolytes, specially molten salts in thermal batteries and organic polymers in hybrid / electrical vehicles. The experiments in this research were carried in a test cell placed inside a vertical furnace having a real time data acquisition system for temperature and electrochemical data. The stability of many first kind reference electrodes was evaluated in long duration blank tests, being selected the following materials: silver, platinum, nickel and molybdenum. The chosen three- electrode cell configuration was: silver as reference, iron disulphide compacted powder as working electrode and graphite as counter-electrode. The applied methodology was the cyclic linear voltammetry at slow sweep rate (0,002 Vs-1), ensuring quasi equilibrium conditions. For the thermodynamical equilibrium the standard potential determinations for open circuit resulted 0,3306 +- 0,014 V (773 K) with respect to the Ag / AgCl reference. The cathodic transfer coefficient measured to be 0,48 indicates the reversibility of the electrode process and points at its possible application as secondary battery. The FeS2 electrocatalytical behaviour was evaluated though the Tafel curves extracted from the voltammograms. The indicating parameter for this reaction spontaneity, the transfer currents, for this systems were measured to be 14,75 +- 2,73 kA m-2. The evaluation of the reaction intermediaries and products were made allying electrochemical data and characterization techniques. The proposed reaction mechanism is initiated by the reduction of FeS2 to metallic iron as the controlling step, followed by two reactions involving sulphur ions and terminated by the chemical formation of Li2S. A series of chemical and electrochemical processes are proposed to explain formation of intermediary polisulphides, being the most important Li2FeS2 (phase X) spotted here though micrographies displaying it`s characteristic crystals of needle-like morphology.

[pt] A evolução tecnológica e a necessidade de fontes de energia cada vez mais eficientes e compactas alavancam os estudos eletroquímicos, no intuito de desenvolver fontes primárias e secundárias mais duráveis e que suportem uma maior carga de operação. Dentre as fontes eletroquímicas temos as primárias (pilhas) e as secundárias (baterias). A diferença fundamental entre essas fontes é o fato das baterias suportarem um número definido de ciclos de carga-descarga, enquanto as pilhas sofrem um único ciclo de descarga após o qual devem ser descartadas. É importante notar que a fonte deve ser adequada à aplicação para qual foi desenvolvida. Assim, em alguns casos especiais, como sistemas de emergência, aparatos militares e aeroespaciais, são necessárias fontes que possuam longa vida de prateleira, alta confiabilidade e alta densidade de corrente. Nesse contexto, enquadram-se as pilhas térmicas que são fontes primárias, nãorecarregáveis e inertes à temperatura ambiente. No desenvolvimento das pilhas térmicas o sistema de última geração funciona com anodos de liga de Lítio, eletrólitos eutéticos de LiCl-KCl e catodos de FeS2. O objetivo deste trabalho foi estudar uma rota de síntese pirometalúrgica a partir da reação de ustulação sulfetante do Fe2O3 com enxofre vaporizado, para obtenção do FeS2 de alta pureza, utilizado como despolarizante nas pilhas. As variáveis de estudo foram a temperatura e o tempo de reação, além da temperatura de volatilização do enxofre e, para avaliação dos resultados foram realizadas caracterizações dos produtos em MEV e DRX, com auxílio do método quantitativo de Rietveld. Os resultados obtidos mostraram uma conversão próxima de 90 % e uma alta dispersão de tamanho de partículas devido à agregação das mesmas. Todavia, a desagregação manual pode resultar em partículas menores adequadas à fabricação do catodo. / [en] The continuous evolution of new technologies and the requirement for more efficient and compact power sources, justify many electrochemical researches in order to develop new types of primary and secondary power sources achieving longer operational lives and more density of energy. The primary power sources are not capable of running on charges-discharges cycles and because of this have to be discarded after the ending of electrochemical reactions (end of operational life). On the other hand the secondary sources are capable of doing charges cycles and therefore have a longer life. It is very important to realize that each kind of power source should be proper to specific applications. Though, in some cases, like emergency systems, military equipments and air and space features, it is necessary to have long shelf life sources, high reliability and high density of energy. For these special applications some sources called thermal batteries fit very well and these are primary electrochemical sources, non-rechargeable and inert at the room temperature. On the development of thermal batteries there was consolidated the technology that uses lithium-alloy anodes, eutectic salt electrolytes based on LiCl-KCl and FeS2 cathodes. The main goal of this work is to study a pyrometallugical route for the synthesis of high purity FeS2 by the reaction of vaporized sulfur and Fe2O3, for further constructions of thermal batteries prototypes. The variables of the study are temperature and time of reaction, besides the volatilizing temperature of sulfur. The analysis was done by MEV and XRD within the Rietveld method. The results showed almost 90% but a high dispersion of particles sizes. It is expected to obtain less dispersion of sizes by disaggregation methods.

In this work new novel cathode materials such as transition-metal sulfides, chlorides or fluorides were investigated and studied for their use in lithium ion thermal batteries. All cathodes were synthesized by a solid state reaction in sealed quartz tubes with a duration of firing for 1 week at high temperatures ( > 500 °C). All structures of compounds were probed by powder X-ray diffraction and the morphology and shape of crystallites of cathodes were characterized by scanning electron microscopy. The electrochemical properties of the batteries were investigated by galvanostatic discharge and galvanostatic intermittent titration technique at high temperatures (> 400 °C). All the batteries used as an anode Li₁₃Si₄, as an electrolyte LiCl-KCl eutectic and as separator MgO. All the products of the discharge mechanism were confirmed using powder X-ray diffraction and EDX analysis. CoNi₂S₄ and NiCo₂S₄ exhibit two voltage plateaux vs Li₁₃Si₄ at 500 °C, one at around 1.75 V and the second at 1.50 V. Capacities of 350 and 290 mA h g⁻¹ were achieved, respectively. NiS, Co₃S₄ and Co₉S₈ were confirmed as the products of discharge mechanism. ZrS₃ exhibits a single flat voltage plateau of 1.70 V at a current density of 11 mA/cm² and a capacity of 357 mA h g⁻¹, at 500 °C was obtained. A new material, LiZr₂S₄, was identified as the product of the electrochemical process, which can be indexed to a = 10.452(8) Å cubic unit cell. KNiCl₃ was tested at different current densities from 15 mA/cm² to 75 mA/cm² and a high cell voltage, with a capacity of 262 mA h g⁻¹ was achieved at 425 °C. Ni metal, KCl and LiCl were confirmed as the products of the discharge mechanism. Li₂MnCl₄ was tested at the same current densities as KNiCl₃ at 400 °C and a capacity of 254 mA h g⁻¹ was achieved. Mn metal and LiCl were confirmed as the products after discharge. Li₆VCl₈ has a capacity of 145 mA h g⁻¹ and a flat voltage plateau of 1.80 V at 500 °C. NiCl₂ has also a capacity of 360 mA h g⁻¹ and a high voltage profile of 2.25 V at 500 °C. CoCl₂ exhibits a lower capacity of 332 mA h g⁻¹ and lower voltage profile compared to NiCl₂ at 500 °C. CuF₂ and PbF₂ were tested at 500 °C. PbF₂ exhibits a single flat voltage plateau of 1.25 V and a capacity of 260 mA h g⁻¹ was obtained. CuF₂ has a high voltage profile but a voltage plateau could not be obtained.

Electrolyte and pyrotechnic pellets are two important components of thermal batteries. Both electrolyte and pyrotechnic pellets are produced by cold compaction of constituent powders. These compacts are integrated in the battery as pellets with sufficient green density, green strength, calorific energy and burning rate (for pyrotechnic only) to provide high performance batteries. In this study, effects of physical properties of the used powders such as particle size distribution, average particle size, particle shape and composition of components and applied compression pressure and their interactions on green density and green strength of electrolyte pellets and in addition, calorific energy and burning rate of pyrotechnic pellets were examined. Statistical experimental designs were constructed to investigate the main and interaction effects of studied variables. 24 two factorial statistically designed experiments&rsquo / results for pyrotechnic pellets exhibited that the compression pressure and iron powder morphology were the most significant factors improving green density and break strength of pyrotechnic pellets. It was shown that the compression pressure had a negative effect on burning rate. Both calorific output and burning rate were increased significantly by increasing KClO4 fraction. In addition, decreasing particle size of KClO4 had also a positive effect on burning rate. The maximum calorific output was obtained at maximum KClO4 fraction. 23 two factorial statistically designed green strength and green density experiments&rsquo / results of electrolyte pellets revealed that, compression pressure was again the dominating factor. Moreover, there was a tendency for higher green density with lower MgO fraction and electrolyte powder average particle size. Besides, the positive effect of decreasing average particle size on green strength was investigated distinctly at low green density values. From the thermal battery perspective, main and interaction effects of variables on the characteristics of electrolyte and pyrotechnic pellets were successfully examined.