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Figure 9. Working Principles and Architectures of Photochargeable RFBs (A) Working principle of a single-photocatalyst-driven photochargeable RFBs based on the BiVO4 photoanode. Reprinted with permission from Zhou et al.16 Copyright 2018 Wiley-VCH Verlag GmbH & Co. KGaA. (B) Schematic illustration of a dual-photoelectrode-driven photochargeable RFBs with Ta3N5 as the photoanode and GaN/Si as the photocathode. Reprinted with permission from Cheng et al.88 2017 Wiley-VCH Verlag GmbH & Co. KGaA. (C and D) Schematic of a photoassisted chargeable RFB with the TiO2 photoanode (C) and the corresponding potential diagram for the photoassisted charging process (D). Reprinted with permission from Li et al.91 2016 Wiley-VCH Verlag GmbH & Co. KGaA. couples in the catholyte and anolyte, respectively; it achieved a stable photocharge- able RFB with a SOEE up to 1.23%.16 In summary, integrating low-cost and high-per- formance photoelectrodes maintaining high solar energy conversion efficiency and high stability with advanced RFBs possessing fast redox reactions should be the focus of future research. MEMBRANE-FREE RFBs Membrane is one of the most important components in commercial RFBs. Almost all performance metrics, including cycle life, Coulombic efficiency, voltage efficiency, power density, and capacity utilization, are affected by membranes. In aqueous RFBs, Nafion, a sulfonated-tetrafluoroethylene-based copolymer, is the most widely used membrane. In the molecular structure of Nafion, the sulfonate ion clusters are held within the rigid fluorocarbon framework. The fast ionic conductivity relies on the hopping mechanism of cations from sulfonate sites one by one, and the selectivity is mainly enabled by Donnan exclusion. Given the special structure and the resulting costly manufacturing processes, Nafion is the most expensive component in a vana- dium RFB in that it accounts for nearly 40% of the total cost. In this aspect, designing membrane-free RFBs represents a promising approach to substantially decreasing the stack cost of RFBs. The membrane-free concepts are typically enabled by engi- neering the fluid mechanics of catholytes and anolytes or fine tuning of the interfacial reactions. The first concept of membrane-free RFB can be traced back to 2002, when Whitesides and coworkers built a millimeter-scale vanadium battery omitting a membrane by exploiting the laminar flow at low Reynolds number so as to eliminate the convective mixing of the catholyte and anolyte.93 Buie and coworkers proposed 1982 Chem 5, 1964–1987, August 8, 2019PDF Image | Development of Redox Flow Batteries Based on New Chemistries
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