1 |
The effect of temperature on phase transformation mechanisms in electrodes for Li-ion batteriesMeng, Wei January 2018 (has links)
The effect of elevated temperatures on the phase transformation mechanisms in electrodes for lithium-ion batteries (LIBs) is an important but – to date – only less studied subject in battery research. In real-life applications, LIBs usually function at non-ambient conditions and especially increased temperatures give rise to safety concerns. This thesis focuses to gain deeper insights into the phase transformations at high temperatures (HTs) by tackling both the challenging hardware development of a HT in situ synchrotron X-ray diffraction (XRD) battery testing system as well as its application to study two important cathode materials: LiFePO4 and V6O13. This allows unprecedented insights into the structural changes and its influence on electrochemical performance at variable temperatures (VTs). LiFePO4 was investigated for various battery cycling rates and temperatures. Electrochemical cycling of LiFePO4 in the newly designed in situ XRD setup proved that the in situ XRD cells work from low to high cycling rates between 25 to 150oC. The current induced non-equilibrium solid solution metastable LiFePO4 phase, present at room temperature during high rate cycling, was found to be less pronounced at temperatures above 125oC. This is possibly due to faster Li-ion diffusion at HT, leading to faster phase separations in the solid solution phases. In a next step, V6O13, a promising cathode material for HT applications, especially for oil field applications, was tested using the in situ HT XRD setup. The material exhibits a very high capacity with a complex voltage profile. The underlying asymmetric discharge and charge phase transition mechanisms, which include a six-step discharge and five-step charge process, are unravelled by in situ XRD. The LixV6O13 unit cell expands sequentially in c, b, and a directions during discharge and reversibly contracts back during charge. The process is associated with a change of occupied lithium sites as well as charge ordering in LixV6O13. Density functional theory (DFT) calculations and nuclear magnetic resonance spectroscopy gave further insight into the electronic structures and preferred Li positions in the different structures formed upon cycling, particularly at high lithium contents. At HT, V6O13 exhibits an even greater capacity, as well as a more symmetric discharge and charge profile. Combining the results from the HT in situ XRD study and the DFT calculation, the most Li puckered phase was found to be able to open further along the b axis, with a new Li site getting (partially) occupied. The new Li site corresponds to more Li intercalation into the LixV6O13 structure and, therefore, more electrode charge storage capacity. The more symmetric discharge and charge process was attributed to the disappearance of phase 2 (present at room temperature for 1.7 < x ≤ 2.1 in LixV6O13) at HT.
|
2 |
Transfert d'eau et de chaleur dans une pile à combustible à membrane : mise en évidence expérimentale du couplage et analyse des mécanismes / Heat and water transfer in a proton exchange membrane fuel cell : experimental demonstration and analysis of coupling mechanismsThomas, Anthony 23 November 2012 (has links)
Les piles à combustible à membrane échangeuse de protons (PEMFC) permettent de convertir efficacement de l'énergie chimique en électricité. Pour cela l'hydrogène s'oxyde sur une des électrodes de la pile, les protons ainsi créés traversent l'électrolyte (membrane) tandis que les électrons parcourant le circuit extérieur fournissent l'énergie électrique. Tous ces éléments se recombinent à la seconde électrode qui, à l'aide de la réduction de l'oxygène, va former de l'eau. Le rendement n'étant pas parfait, une partie de l'énergie des réactifs est aussi dégradée sous forme de chaleur. Malgré de récents progrès, la commercialisation à grande échelle des piles à combustible est toujours entravée par des problèmes de durabilité, liés notamment à la gestion de l'eau et de la température au sein de ce système. Afin de quantifier le comportement thermique et son effet sur le transport de l'eau, une pile à combustible a été instrumentée, permettant la mesure de la température aux électrodes, des flux de chaleur et d'eau. Les résultats montrent que de forts gradients de température (jusqu'à environ 30 K/mm) peuvent exister pour une pile fonctionnant dans des conditions standard. Il a été observé une nette influence du champ de température dans le coeur de pile sur le transport de l'eau qui se fait vers la partie la plus froide de la pile (généralement les canaux d'alimentation), l'eau traversant les couches de diffusion poreuses sous forme vapeur dans nos conditions expérimentales / Proton exchange membrane fuel cells (PEMFC) make it possible to convert efficiently chemical energy into electricity. For this, hydrogen is oxidized at one of the electrodes of the cell, created protons pass through the electrolyte (membrane) while electrons flow across the external circuit provide the electrical energy. All these elements recombine at the second electrode, with oxygen, to produce water. Performance is not perfect within a cell and a part of the reactants energy is also degraded as heat. Despite recent advances, the large scale commercialization of PEMFC is still hampered by durability issues, some of them being related to water and thermal management. In order to quantify the thermal behavior and its effect on the water transport, a fuel cell has been instrumented for the electrodes temperature, water and heat fluxes measurement. The results show that high temperature gradients (up to about 30 K/mm) can exist in a cell operating under standard conditions. It was observed a clear influence of the temperature field in the cell on the water transport. Water flows towards the coldest part of the cell (usually the channels), passing through the porous layers in vapor phase in our experimental conditions
|
Page generated in 0.0671 seconds