The commercial deployment of wireless photoelectrochemical cells (PECs) may provide a viable means to close the anthropogenic carbon cycle associated with the global transportation sector. The growing body of research on PECs has largely focused on developing and integrating the materials necessary for robust, efficient solar-fuel production on the laboratory benchtop. While these efforts are a prerequisite for the commercialization of PECs, deployed PECs will have to contend with extreme heat, cold, and insolation variations in the outdoor environment. They will also have to operate efficiently throughout their lifetime and in multiple locations. This paper reports a computational framework for estimating the hourly profiles of time-varying temperature and solar-to-hydrogen efficiency that optically concentrating, wireless PECs will attain over the course of a typical year. It is found that annual weighted average solar-to-hydrogen efficiencies in excess of 9 to 11% can be achieved in extremely cloudy and sunny locations, respectively. Additionally, typical PECs will likely incur damage due to overheating or freezing; measures to protect PECs from extreme heat and cold are outlined. The findings also help to bring into focus issues regarding real-world deployment of energy-generation technologies and methodologies towards tackling them.

Membrane-encapsulated devices are attractive for solar-driven hydrogen production, as their design mitigates problems with concentration overpotentials, gas bubbles, and safety inherent in liquid electrolyte water-splitting devices. However, the competing processes such as heat, water, gas, and ion transport make it nontrivial to design such devices. Here, we show analytical expressions and associated design spaces for critical membrane dimensions and material properties required for stable and efficient gas, heat, proton, and water transport. The best condition for stable gas transport in thin film or gas channels is given by the critical Damköhler number. The maximum heating of the device is governed by the Heating and Nusselt numbers, which can be tuned to the desired level. The optimal dimensions of the device, to operate under tolerable ohmic losses, correspond to the maximum value of scaled Power-loss factor. An optimal device architecture is proposed for stable and efficient operation. © 2014 The Electrochemical Society.

The hydrogen energy provided by solar-driven photoelectrochemical (PEC) water splitting must be greater than the energy used to produce and operate the technology, as a fundamental system requirement to enable energetic benefits to society. PEC H2 production will require significant advances from both basic scientific research and applied technology development, prior to manufacturing and field deployment. To identify opportunities and priorities, here we use prospective life cycle system modeling to investigate the net-energy significance of six characteristics describing the PEC life cycle: (1) embodied energy of active cell materials, (2) embodied energy of inactive module materials, (3) energy intensity of active cell fabrication, (4) energy intensity of PEC module assembly, (5) initial energy use for production of balance-of-system (BOS), and (6) ongoing energy use for operation and end-of-life of BOS. We develop and apply a system model describing material and energy flows during the full life cycle of louvered thin-film PEC cells and their associated modules and BOS components. We find that fabrication processes for the PEC cells, especially the thin-film deposition of active cell materials, are important drivers of net energy performance. Nevertheless, high solar-to-hydrogen (STH) conversion efficiency and long cell life span are primary design requirements for PEC systems, even if such performance requires additional energy and material inputs for production and operation. We discuss these and other system dynamics, and highlight pathways to improve net energy performance.

An integrated cell for the solar-driven splitting of water consists of multiple functional components and couples various photoelectrochemical (PEC) processes at different length and time scales. The overall solar-to-hydrogen (STH) conversion efficiency of such a system depends on the performance and materials properties of the individual components as well as on the component integration, overall device architecture, and system operating conditions. This Review focuses on the modeling- and simulation-guided development and implementation of solar-driven water-splitting prototypes from a holistic viewpoint that explores the various interplays between the components. The underlying physics and interactions at the cell level is are reviewed and discussed, followed by an overview of the use of the cell model to provide target properties of materials and guide the design of a range of traditional and unique device architectures.