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Engineering nanoscale polymers in photovoltaics and supercapacitors: experimental and theoretical studies
Dissertation   Open access

Engineering nanoscale polymers in photovoltaics and supercapacitors: experimental and theoretical studies

Yuriy Smolin
Doctor of Philosophy (Ph.D.), Drexel University
Jun 2017
DOI:
https://doi.org/10.17918/etd-7356
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Abstract

Dye-sensitized solar cells Polyelectrolytes Chemical Engineering Chemical Vapor Deposition Polymer Chemistry
Dye sensitized solar cells (DSSCs) and carbon-based supercapacitors are promising energy conversion and storage systems, respectively, because they can be made inexpensively, have good performance, and can be integrated into portable and flexible electronics. Both systems utilize nanostructured porous electrodes, leading to fewer diffusion limitations and higher active surface areas for interfacial processes compared to planar electrodes. A major drawback of the DSSC design is the use of a liquid electrolyte, since it is prone to leakage and evaporation-hindering DSSC applications, durability, and thermal stability. A polymer electrolyte (PE) can overcome these shortcomings; however, the integration of a PE within the mesoporous TiO2 photoanode of DSSCs with pore openings of 10-20 nm and photoanode thicknesses of ~10 [mu]m is very challenging. Solution-based deposition methods such as spin coating and drop casting to deposit PEs has led to incomplete pore filling inside the mesoporous photoanode, resulting in lower than optimal efficiencies. To overcome these challenges, a solvent-free method called initiated chemical vapor deposition (iCVD) was adopted to deposit PEs within the porous TiO2 electrode. In iCVD, the monomer and initiator are vapors which easily penetrate into the porous electrode. By carefully controlling the iCVD processing parameters, complete pore filling of PEs into the TiO2 photoanode was achieved, leading to 50% improvement in conversion efficiency. Polymers with ether, ester, pyridine, pyrrolidone, imidazole and epoxy functionality were synthesized and integrated. The findings indicated that DSSC characteristics, including open circuit voltage, short circuit current density and fill factor, can be tuned by polymer chemistry. A promising approach to improve the energy density of supercapacitor electrodes is to integrate inexpensive conducting polymers (CPs), such as polyaniline (PANI). Unfortunately, most CPs are insoluble, and integrating CPs into tortuous electrode pores with aspect ratios of >10,000 while preserving the intrinsic pore structures, to retain the double layer capacitance, is very challenging. Therefore, similarly to the iCVD process, oxidative CVD (oCVD) was chosen to bypass the limited solubility of CPs to deposit thin conformal CP films onto porous electrodes. By controlling the oCVD deposition parameters, PANI films on the order of a few nm were integrated into carbide-derived-carbon (CDC) electrodes, leading to a doubling of the capacitance. This yielded a PANI-only capacitance of ~690 F/g, close to the theoretical value of 750 F/g. This work also combined experiments with first-principles modeling to develop a model-guided design and optimization framework, allowing for optimal device design and the intelligent selection of polymer chemistries with minimal experimental investigations. For example, to determine the effects of PE chemistry on DSSC processes, parameter estimation and parametric sensitivity studies were conducted which indicated that a shift in the conduction band of TiO2 and a suppression of the back electron transfer at the dye-TiO2-PE interface was induced by the side group PE chemistry. Furthermore, optimal design specifications for a PE DSSC were calculated using the model, and optimally performing DSSCs were subsequently fabricated and tested, validating the model.

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