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DETECTION OF SUPEROXIDE ANION RADICALS IN ANION EXCHANGE MEMBRANE FUEL CELLS USING IN-SITU FLUORESCENCE SPECTROSCOPY
Title
DETECTION OF SUPEROXIDE ANION RADICALS IN ANION EXCHANGE MEMBRANE FUEL CELLS USING IN-SITU FLUORESCENCE SPECTROSCOPY
Creator
Zhang, Yunzhu
Date
2016, 2016-07
Description
Anion exchange membrane (AEM) stability is a long-standing challenge that has limited the widespread development and adoption of AEM fuel...
Show moreAnion exchange membrane (AEM) stability is a long-standing challenge that has limited the widespread development and adoption of AEM fuel cells. It is essential to understand the mechanism of AEM degradation during fuel cell operation. There are multiple modes of AEM degradation, broadly classified as chemical, mechanical and thermal degradation. Chemical degradation is among the most destructive modes, and can be further sub-divided into nucleophilic degradation (induced by the hydroxide ion), and oxidative degradation (induced by reactive oxygen species). While the former has been extensively studied, there is minimal work on oxidative AEM degradation. The reactive oxygen chemical species produced during the operation of an AEM fuel cell have hitherto not been detected during operation. Given the high pH, it is postulated that superoxide anion radicals (𝑂2∙−), as opposed to hydroxyl radicals, are primarily involved in the degradation progress. The objective of this study was to confirm the 𝑂2∙− formation during AEM fuel cell operation and to monitor in real-time the rate of 𝑂2∙− generation in an operating fuel cell using in-situ fluorescence spectroscopy. 1,3-diphenlisobenzofuran (DPBF) was chosen as the fluorescence probe, the sensitivity of which towards 𝑂2∙− was evaluated by performing ex-situ experiments in a semi-batch reactor. We demonstrate that the fluorescence intensity of this dye selectively decreased upon exposing 𝑂2∙−. DPBF was then incorporated into an AEM (membrane was solution cast after mixing the dye with the casting solution), which was assembled into a fuel cell. 𝑂2∙− generation in an operating AEM fuel cell was then monitored via in-situ fluorescence spectroscopy using a bifurcated optical probe, when the cell was operated in H2/O2 mode. To confirm the impact of 𝑂2∙− on AEM degradation, independent experiments (without dye) were performed under identical conditions, under both H2/O2 and N2/N2 modes, and the ionic conductivity and ion exchange capacity were monitored to estimate degradation extent. From our in-situ fluorescence studies, we were able to estimate the rate constants and activation energy for oxidative AEM degradation in an operating AEM fuel cell.
M.S. in Chemical Engineering, July 2016
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INVESTIGATION OF OXYGEN GENERATION DURING THE OPERATION OF LITHIUM-ION CELLS USING IN-SITU FLUORESCENCE SPECTROSCOPY
Title
INVESTIGATION OF OXYGEN GENERATION DURING THE OPERATION OF LITHIUM-ION CELLS USING IN-SITU FLUORESCENCE SPECTROSCOPY
Creator
Li, Mo
Date
2016, 2016-07
Description
An ex-situ fluorescence spectroscopy system was set up and utilized to study the interaction of fluorescent dyes with an oxygen quencher. The...
Show moreAn ex-situ fluorescence spectroscopy system was set up and utilized to study the interaction of fluorescent dyes with an oxygen quencher. The Stern-Volmer relationship was obtained and fitted to correlate the partial pressure of oxygen to the dye fluorescence intensity. The oxygen quenching constant ι for 30 ΞM 9,10-dimethylanthracene_(DMA) dissolved in the mixture of ethylene carbonate_(EC) and dimethyl carbonate_(DMC) (1:1 volume ratio) were 0.69/0.62 at high/low partial pressure of oxygen. Operation of the self-made pouch cells with LiCoO2 as the cathode material was examined by charging/discharging at C/10. The discharge capacities were 107 and 104 mAh/g for the pouch cell both with and without the optical probe, which indicates that the optical probe did not significantly affect the performance and capacity of the cell. The optical probe was inserted into the pouch cell to measure the fluorescence intensity of the dye that was dissolved in the electrolyte. Time series experiments before charging demonstrated that the fluorescence intensity was stable for at least 24 hours. However, the fluorescence intensity decreased abruptly as the voltage of the pouch cell increased during the initial stages of charging, which means that the dye (DMA) could not be employed to detect the oxygen generated in the cell. Both the real-time fluorescence spectroscopy and the cyclic voltammetry illustrated that this dye was not suitable for the in-situ fluorescence tests. The electrochemical stability at room temperature of different dyes such as anthracene, Palladium (II) meso-tetrakis (pentafluorophenyl porphyrin)_(PTTFPP) and Platinum octaethylporphyrin_(PtOEP) were examined in the organic solvents used in the electrolytes in Li-ion cells. Cyclic voltammograms of anthracene and PTTFPP showed oxidation peaks at 2V and reduction peaks at around 1V, with the possible formation of the radical anion causing spectral changes. The chemical compound 1-hexyl-3- methylimidazolium bis (trifluormethylsulfonyl)imide_(HMIM BTI) was electrochemically stable, but the fluorescence intensity was too low (5% of dye DMA) to be used in the in-situ detection of oxygen. As a result, more work must be performed in the future to find a suitable dye. Keywords: fluorescence spectroscopy, in-situ Li-ion cell operation, quencheroxygen, the Stern-Volmer relationship
M.S. in Chemical Engineeering, July 2016
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