Achieving high current densities without thermal performance degradation at high temperatures is one of the main challenges for enhancing the competitiveness of photo-electrochemical energy storage systems. We describe a system that overcomes this challenge by incorporating an integrated photoelectrode with a redox flow cell, which functions as a coolant for the excess heat from the photo-absorber. We perform quantitative analyses to theoretically validate and highlight the merit of the system. Practical operation parameters, including daily temperature and redox reaction kinetics, are modeled with respect to heat and charge transfer mechanisms. Our analyses show a profound impact on the resulting solar-to-chemical efficiencies and stored power, which are 21.8% higher than that of a conventional photovoltaic-assisted energy storage system. This paves the way for reassessing the merit of photovoltaic-integrated systems, which have hitherto been underrated as renewable energy storage systems.@en

In recent years, solar redox flow batteries have attracted attention as a possible integrated technology for simultaneous conversion and storage of solar energy. Unlike solar water splitting technologies which require at least 1.8V for meaningful performance, a lesson learned from previous solar redox flow battery (SRFB) studies is that even single-photon-devices can demonstrate unbiased photo-charging owing to the flexibility of redox couple selection. Thus, in this paper, we present the theoretical model reflecting experimental parameters, such that we can highlight important parameters that merit the most attention in further studies towards the practical development of SRFBs. Importantly, the results clearly show how to choose the optimum combination of semiconductor and redox couples under unavoidable limitations that a practical system would encounter, including, but not limited to optical loss by the electrolyte, overpotential, device architecture and chemical potentials.@en