Abstract

Two designs for an integrated photoelectrolysis system that uses a 10× concentrating solar collector have been investigated in detail. The system performance was evaluated using a multi-physics model that accounted for the properties of the tandem photoabsorbers, mass transport, and the electrocatalytic performance of the oxygen-evolution and hydrogen-evolution reactions (OER and HER, respectively). The solar-to-hydrogen (STH) conversion efficiencies and the ohmic losses associated with proton transport in the solution electrolyte and through the membrane of the photoelectrolysis system were evaluated systematically as a function of the cell dimensions, the operating temperatures, the bandgap combinations of the tandem cell, and the performance of both the photoabsorbers and electrocatalysts. Relative to designs of optimized systems that would operate without a solar concentrator, the optimized 10× solar concentrator designs possessed larger ohmic losses and exhibited less uniformity in the distribution of the current density along the width of the photoelectrode. To minimize resistive losses while maximizing the solar-to-hydrogen conversion efficiency, ηSTH, both of the designs, a two-dimensional “trough” design and a three-dimensional “bubble wrap” design, required that the electrode width or diameter, respectively, was no larger than a few millimeters. As the size of the electrodes increased beyond this limiting dimension, the ηSTH became more sensitive to the performance of the photoabsorbers and catalysts. At a fixed electrode dimension, increases in the operating temperature reduced the efficiency of cells with smaller electrodes, due to degradation in the performance of the photoabsorber with increasing temperature. In contrast, cells with larger electrode dimensions showed increases in efficiency as the temperature increased, due to increases in the rates of electrocatalysis and due to enhanced mass transport. The simulations indicted that cells that contained 10% photoabsorber area, and minimal amounts of Nafion or other permselective membranes (i.e. areal coverages and volumetric fractions of only a few percent of the cell), with the remaining area comprised of a suitable, low-cost inert, non porous material (flexible polymers, inert inorganic materials, etc.) should be able to produce high values of ηSTH, with ηSTH = 29.8% for an optimized design with a bandgap combination of 1.6 eV/0.9 eV in a tandem photoabsorber system at 350 K.

Highlights

  • Concentrated photovoltaics (CPV) typically incorporate multi-stage optical systems to achieve high optical concentration (∼ 400 Suns to 1200 Suns),[8,9,10] integrated photoelectrochemical systems for large scale, distributed solar-to-fuel applications are most likely operate efficiently and scalably at lower solar concentration factors (5 – 100) due to limitations associated with electrocatalytic overpotential losses, ohmic losses, and mass transport restrictions associated with high current densities in a system operating under very concentrated sunlight

  • The distribution of the current density along the electrode width was highly non-uniform for this light-concentrating photoelectrolysis system

  • Compared to an unconcentrated system, the oxygen-evolution reaction (OER) overpotential difference between the mid-point and the two ends of the electrode increased from 6.5 mV to 49.4 mV (Figure 3b) and the maximum resistive loss increased from 17.2 mV to 143.1 mV (Figure 3a) with the same electrode width, electrode height and Nafion area

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Summary

Introduction

Artificial photosynthesis could provide a promising route to largescale solar energy conversion and storage.[1,2,3,4] Recent techno-economic studies have evaluated various designs for integrated photoelectrolysis systems, including a very promising system that makes use of concentrated illumination.[5,6] A discrete III-V photovoltaic cell connected electrically in series with a discrete polymer-electrolyte membrane (PEM) electrolyzer has demonstrated a solar-to-hydrogen (STH) conversion efficiency of 18% under 500 Suns.[7] concentrated photovoltaics (CPV) typically incorporate multi-stage optical systems to achieve high optical concentration (∼ 400 Suns to 1200 Suns),[8,9,10] integrated photoelectrochemical systems for large scale, distributed solar-to-fuel applications are most likely operate efficiently and scalably at lower solar concentration factors (5 – 100) due to limitations associated with electrocatalytic overpotential losses, ohmic losses, and mass transport restrictions associated with high current densities in a system operating under very concentrated sunlight.

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