Physical Modeling of Photoelectrochemical Hydrogen Production Devices

Solar-powered water splitting with photoelectrochemical (PEC) devices is a promising method to simultaneously harvest and store solar energy at a large scale. Highly efficient small prototype PEC devices reported recently demonstrate a move from basic material research toward design and engineering of complete devices and systems. The increased interest in engineering calls for a better understanding about the operational details of PEC devices at different length scales. The relevant physical phenomena and the properties of typical materials are well-known for separate device components, but their interaction in a complete PEC cell has received less attention. Coupled physical models are useful for studying these interactions and understanding the device operation as a whole and for optimizing the devices. We review the central physical processes in solar-powered water splitting cells and the physical models used in their theoretical simulations. Our focus is in particular on how different physical processes have been coupled together to construct device models and how different electrode and device geometries have been taken into account in them. Reflecting on the literature we discuss future opportunities and challenges in the modeling of PEC cells.Peer reviewe

Theoretical Study on Thin Film Dye Sensitized Photovoltaic Solar Cells

This thesis presents two models of a dye-sensitized solar cell (DSC): diffusion model and electrical model. The main purpose is to investigate interfacial charge transfer and charge transport within the semiconductor/electrolyte layer under illuminated conditions. These two interrelated models confirm that diffusion is the major driving force for electron and ion transport, while the drift of electrons is negligible. The diffusion model was utilized to simulate the temperature influence on the overall efficiency of DSC with a consideration of the voltage loss at titanium dioxide (TiO2)/ transparent conductive oxide (TCO) interface. It reveals that low temperature conditions have serious detrimental effects on the DSCs' performance. Further the electrical model was used to analyze the effect of diffusion/drift, dye loading, and electrode thickness on DSC performance. The predicted optimal electrode thickness ranges between 10-15 μm which is consistent with the thickness (10 μm) used in experimental studies published in the literature

Nanostructured Thin Film Synthesis by Aerosol Chemical Vapor Deposition for Energy Storage Applications

Renewable energy sources offer a viable solution to the growing energy demand while mitigating concerns for greenhouse gas emissions and climate change. This has led to a tremendous momentum towards solar and wind-based energy harvesting technologies driving efficiencies higher and costs lower. However, the intermittent nature of these energy sources necessitates energy storage technologies, which remain the Achilles heel in meeting the renewable energy goals. This dissertation focusses on two approaches for addressing the needs of energy storage: first, targeting direct solar to fuel conversion via photoelectrochemical water-splitting and second, improving the performance of current rechargeable batteries by developing new electrode architectures and synthesis processes. The aerosol chemical vapor deposition (ACVD) process has emerged as a promising single-step approach for nanostructured thin film synthesis directly on substrates. The relationship between the morphology and the operating parameters in the process is complex. In this work, a simulation based approach has been developed to understand the relationship and acquire the ability of predicting the morphology. These controlled nanostructured morphologies of TiO2, compounded with gold nanoparticles of various shapes, are used for solar water-splitting applications. Tuning of light absorption in the visible-light range along with reduced electron-hole recombination in the composite structures has been demonstrated. The ACVD process is further extended to a novel single-step synthesis of nanostructured TiO2 electrodes directly on the current collector for applications as anodes in lithium-ion batteries, mainly for electric vehicles and hybrid electric vehicles. The effect of morphology of the nanostructures has been investigated via experimental studies and electrochemical transport modelling. Results demonstrate the exceptional performance of the single crystal one-dimensional nanostructures over granular structures, due to a combination of high surface area, improved lithium diffusivity and electronic conductivity. The model developed allows for the prediction of optimized nanostructure geometry depending on the end-use application. Increasing demand for lithium-ion batteries, posing concerns for lithium supply and costs in future, have motivated research in sodium-ion batteries as alternatives. In this work, the nanostructured TiO2 electrodes have been studied as anodes for sodium ion batteries. To improve the performance, a new multi-component ACVD process has been developed to achieve single-step synthesis of doped nanostructured thin films. One-dimensional niobium doped TiO2 thin films have been synthesized and characterized as a novel anode material for sodium-ion batteries. The doped nanostructured thin films deliver significant improvements on capacity over their undoped counterparts and demonstrate feasibility of sodium-ion batteries. In summary, the studies conducted in this dissertation develop a detailed understanding of the ACVD process and demonstrate its ability to synthesize superior nanostructured thin films for energy storage applications, thereby motivating process scalability for commercial applications

How Voltage Drops are Manifested by Lithium Ion Configurations at Interfaces and in Thin Films on Battery Electrodes

Battery electrode surfaces are generally coated with electronically insulating solid films of thickness 1-50 nm. Both electrons and Li+ can move at the electrode-surface film interface in response to the voltage, which adds complexity to the "electric double layer" (EDL). We apply Density Functional Theory (DFT) to investigate how the applied voltage is manifested as changes in the EDL at atomic lengthscales, including charge separation and interfacial dipole moments. Illustrating examples include Li(3)PO(4), Li(2)CO(3), and Li(x)Mn(2)O(4) thin-films on Au(111) surfaces under ultrahigh vacuum conditions. Adsorbed organic solvent molecules can strongly reduce voltages predicted in vacuum. We propose that manipulating surface dipoles, seldom discussed in battery studies, may be a viable strategy to improve electrode passivation. We also distinguish the computed potential governing electrons, which is the actual or instantaneous voltage, and the "lithium cohesive energy" based voltage governing Li content widely reported in DFT calculations, which is a slower-responding self-consistency criterion at interfaces. This distinction is critical for a comprehensive description of electrochemical activities on electrode surfaces, including Li+ insertion dynamics, parasitic electrolyte decomposition, and electrodeposition at overpotentials.Comment: 35 pages. 10 figure

(Photo)Electrocatalytic CO2 Reduction at the Defective Anatase TiO2 (101) Surface

Excessive carbon dioxide (CO2) emissions by combustion of fossil fuels are linked to global warming and rapid climate change. One promising route to lowering the concentration of CO2 in the atmosphere is to reduce it to useful small molecules via photoelectrocatalytic hydrogenation, which would enable solar energy storage with a zero-carbon emission cycle and perform a more efficient separation of the photogenerated electron and hole pair than pure photocatalysis. Indeed, photoelectrocatalytic CO2 reduction has been an intense focus of research. Using the density functional theory (DFT), we studied the CO2 reduction reaction on the defective anatase TiO2 (101) surface, at both the solvent/catalyst and the electrolyte/catalyst interfaces. The analysis of the electronic structure of the surface shows a contrast between the solvent/catalyst and the electrolyte/catalyst interfaces, which results in the two corresponding catalytic cycles being distinct. Our study explains at the electronic and mechanistic levels why methanol is the main product in the presence of the electrolyte and why the overpotential is not only controlled by the reaction process but also by the diffusion process