An Experimental and Technoeconomic Study of Silicon Microwire Arrays for Fuel Production Using Solar Energy

Direct solar energy conversion is one of few sustainable energy resources able to wholly satisfy global energy demand; however, utility scale adoption and reliance are currently limited by the lack of a cost effective energy storage technology. The production of fuel from sunlight (solar fuels) enables solar energy storage in chemical bonds, a volumetrically and gravimetrically dense form compatible with current infrastructure worldwide. Hydrogen production via water splitting is a first generation solar fuel targeted herein that is currently used for hydrocarbon up-grading and fertilizer production and could further be utilized in combustion cycles and/or fuel cells for electricity and heat production and transportation. This thesis presents achievements that form the foundation for Si microwire array based solar water splitting devices beginning with a tandem junction device design using Si microwire arrays as the architectural motif and one of many active components. Si microwire arrays have potential advantages over two dimensional planar device architectures such as minimized resistance losses, lower semiconductor material usage, and embedment in a polymeric membrane enabling a flexible device. Experimental fabrication and characterization of this tandem junction device design was realized in the form of a np+-Si microwire array coated by either tungsten oxide (WO3) or titanium dioxide (TiO2) as the second tandem semiconductor. The Si/TiO2 device demonstrated the highest performance with an expected solar-to-hydrogen efficiency of 0.39%. To achieve these demonstrations new processing methods were needed and developed for formation of the np+-Si microwire array homojunction and formation of a low resistance contact between the p+-Si and second semiconductor using sputtered tin- doped indium oxide (ITO) and spray pyrolyzed fluorine-doped tin oxide (FTO). Another achievement includes demonstration of the longest known (>2200 hours) photoanode stability for water oxidation using a np+-Si microwire array coated with an in-house developed amorphous TiO2 protection layer and NiCrOx electrocatalyst. Additionally, the Si microwire array architecture was used to enable decoupling of semiconductor light absorption and catalytic activity, two performance metrics that ideally are maximized simultaneously. However, all previous demonstrations have shown anti-correlation between these performance metrics because planar architectures are subject to a trade-off where adding electrocatalyst increases catalytic activity, but decreases semiconductor light absorption and vice versa. Finally, a techno-economic analysis of solar water splitting production facilities was performed to assess economic competitiveness because this is the ultimate metric by which all energy production technologies are currently evaluated. This analysis suggests that a hydrogen production facility that is cosmetically similar to current solar panel installations with hydrogen collection from distributed tilted panels is unlikely to achieve cost competitiveness with fossil fuel derived hydrogen due to the balance of systems costs alone. A cost of CO2 greater than ~$800 (ton CO2)-1 was estimated to be necessary for the least expensive base-case solar-to-hydrogen system to reach price parity with hydrogen derived from steam reforming of methane priced at$3 (MM BTU)-1 ($1.39 (kg H2)-1). Direct CO2 reduction systems were also explored and resulted in even larger challenges than hydrogen production. Accordingly, major facility wide breakthroughs are required to obtain viable economic costs for solar hydrogen production, but the barriers to achieve cost-competitiveness with existing large-scale thermochemical processes for CO2 reduction are even greater.</p

Si/TiO_2 Tandem-Junction Microwire Arrays for Unassisted Solar-Driven Water Splitting

Tandem-junction microwire array photoelectrodes have been fabricated by coating np^+-Si radial homojunction microwire arrays sequentially with fluorine-doped tin oxide (FTO) and titanium dioxide (TiO_2). These photoelectrodes effected unassisted water splitting under simulated 1 Sun conditions with an open-circuit potential (E_(oc)) of −1.5 V vs the formal potential for oxygen evolution, E^(0′)(OH^−/O_2), a current density at E = E^(0′)(OH^−/O_2) of 0.78 mA cm^(−2), a fill factor ( ff ) = 0.51, and a photovoltaic-biased photoelectrochemical ideal regenerative cell efficiency of 0.6%

A comparative technoeconomic analysis of renewable hydrogen production using solar energy

A technoeconomic analysis of photoelectrochemical (PEC) and photovoltaic-electrolytic (PV-E) solar-hydrogen production of 10 000 kg H_2 day^(−1) (3.65 kilotons per year) was performed to assess the economics of each technology, and to provide a basis for comparison between these technologies as well as within the broader energy landscape. Two PEC systems, differentiated primarily by the extent of solar concentration (unconcentrated and 10× concentrated) and two PV-E systems, differentiated by the degree of grid connectivity (unconnected and grid supplemented), were analyzed. In each case, a base-case system that used established designs and materials was compared to prospective systems that might be envisioned and developed in the future with the goal of achieving substantially lower overall system costs. With identical overall plant efficiencies of 9.8%, the unconcentrated PEC and non-grid connected PV-E system base-case capital expenses for the rated capacity of 3.65 kilotons H_2 per year were $205 MM ($293 per m^2 of solar collection area (m_S^(−2)), $14.7 W_(H2,P)^(−1)) and$260 MM ($371 m_S^(−2),$18.8 W_(H2,P)^(−1)), respectively. The untaxed, plant-gate levelized costs for the hydrogen product (LCH) were $11.4 kg^(−1) and$12.1 kg^(−1) for the base-case PEC and PV-E systems, respectively. The 10× concentrated PEC base-case system capital cost was $160 MM ($428 m_S^(−2), $11.5 W_(H2,P)^(−1)) and for an efficiency of 20$9.2 kg^(−1). Likewise, the grid supplemented base-case PV-E system capital cost was $66 MM ($441 m_S^(−2), $11.5 W_(H2,P)^(−1)), and with solar-to-hydrogen and grid electrolysis system efficiencies of 9.8$6.1 kg^(−1). As a benchmark, a proton-exchange membrane (PEM) based grid-connected electrolysis system was analyzed. Assuming a system efficiency of 61% and a grid electricity cost of $0.07 kWh^(−1), the LCH was$5.5 kg^(−1). A sensitivity analysis indicated that, relative to the base-case, increases in the system efficiency could effect the greatest cost reductions for all systems, due to the areal dependencies of many of the components. The balance-of-systems (BoS) costs were the largest factor in differentiating the PEC and PV-E systems. No single or combination of technical advancements based on currently demonstrated technology can provide sufficient cost reductions to allow solar hydrogen to directly compete on a levelized cost basis with hydrogen produced from fossil energy. Specifically, a cost of CO_2 greater than ∼$800 (ton CO_2)^(−1) was estimated to be necessary for base-case PEC hydrogen to reach price parity with hydrogen derived from steam reforming of methane priced at$12 GJ^(−1) ($1.39 (kg H_2)^(−1)). A comparison with low CO_2 and CO_2-neutral energy sources indicated that base-case PEC hydrogen is not currently cost-competitive with electrolysis using electricity supplied by nuclear power or from fossil-fuels in conjunction with carbon capture and storage. Solar electricity production and storage using either batteries or PEC hydrogen technologies are currently an order of magnitude greater in cost than electricity prices with no clear advantage to either battery or hydrogen storage as of yet. Significant advances in PEC technology performance and system cost reductions are necessary to enable cost-effective PEC-derived solar hydrogen for use in scalable grid-storage applications as well as for use as a chemical feedstock precursor to CO_2-neutral high energy-density transportation fuels. Hence such applications are an opportunity for foundational research to contribute to the development of disruptive approaches to solar fuels generation systems that can offer higher performance at much lower cost than is provided by current embodiments of solar fuels generators. Efforts to directly reduce CO_2 photoelectrochemically or electrochemically could potentially produce products with higher value than hydrogen, but many, as yet unmet, challenges include catalytic efficiency and selectivity, and CO_2 mass transport rates and feedstock cost. Major breakthroughs are required to obtain viable economic costs for solar hydrogen production, but the barriers to achieve cost-competitiveness with existing large-scale thermochemical processes for CO_2 reduction are even greater

Experimental demonstrations of spontaneous, solar-driven photoelectrochemical water splitting

Laboratory demonstrations of spontaneous photoelectrochemical (PEC) solar water splitting cells are reviewed. Reported solar-to-hydrogen (STH) conversion efficiencies range from 10% STH efficiency using potentially less costly materials have been reported. Device stability is a major challenge for the field, as evidenced by lifetimes of less than 24 hours in all but a few reports. No globally accepted protocol for evaluating and certifying STH efficiencies and lifetimes exists. It is our recommendation that a protocol similar to that used by the photovoltaic community be adopted so that future demonstrations of solar PEC water splitting can be compared on equal grounds

Two time constants for the binding of proteins to DNA from micromechanical data

Recent experimental advances allow the direct measurement of the force/extension behavior for DNA in the presence of strongly binding proteins. Such experiments reveal information about the cooperative mechanism of protein binding. We have studied the irreversible binding of such proteins to DNA using a simple simulation and present a method for estimating quantitative rate constants for the nucleation and growth of linear domains of proteins bound to DNA. Such rate constants also give information about the relative energetics of the two binding processes. We discuss our results in the context of recent data for the DNA-recA-ATPγs system, for which the nucleation time is 4.7 × 104 min per recA binding site and the total growth rate of each domain is 1400 recA/min

Geophysical constraints on the reliability of solar and wind power in the United States

We analyze 36 years of global, hourly weather data (1980–2015) to quantify the covariability of solar and wind resources as a function of time and location, over multi-decadal time scales and up to continental length scales. Assuming minimal excess generation, lossless transmission, and no other generation sources, the analysis indicates that wind-heavy or solar-heavy U.S.-scale power generation portfolios could in principle provide ∼80% of recent total annual U.S. electricity demand. However, to reliably meet 100% of total annual electricity demand, seasonal cycles and unpredictable weather events require several weeks’ worth of energy storage and/or the installation of much more capacity of solar and wind power than is routinely necessary to meet peak demand. To obtain ∼80% reliability, solar-heavy wind/solar generation mixes require sufficient energy storage to overcome the daily solar cycle, whereas wind-heavy wind/solar generation mixes require continental-scale transmission to exploit the geographic diversity of wind. Policy and planning aimed at providing a reliable electricity supply must therefore rigorously consider constraints associated with the geophysical variability of the solar and wind resource—even over continental scales

Functional integration of Ni–Mo electrocatalysts with Si microwire array photocathodes to simultaneously achieve high fill factors and light-limited photocurrent densities for solar-driven hydrogen evolution

An n+p-Si microwire array coupled with a two-layer catalyst film consisting of Ni–Mo nanopowder and TiO_2 light-scattering nanoparticles has been used to simultaneously achieve high fill factors and light-limited photocurrent densities from photocathodes that produce H_2(g) directly from sunlight and water. The TiO_2 layer scattered light back into the Si microwire array, while optically obscuring the underlying Ni–Mo catalyst film. In turn, the Ni–Mo film had a mass loading sufficient to produce high catalytic activity, on a geometric area basis, for the hydrogen-evolution reaction. The best-performing microwire array devices prepared in this work exhibited short-circuit photocurrent densities of −14.3 mA cm^(−2), photovoltages of 420 mV, and a fill factor of 0.48 under 1 Sun of simulated solar illumination, whereas the equivalent planar Ni–Mo-coated Si device, without TiO_2 scatterers, exhibited negligible photocurrent due to complete light blocking by the Ni–Mo catalyst layer