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Figure 4. Polyhedral representation of conventional types of polioxometalates Energies 2021, 14, 5643 [119]. Copyright 2020, MDPI, adapted from Ref. [127], Copyright 2014, Elsevier. 30 of 45 1 3.4.2. Redox Mediator In order to circumvent the pressure drop issued due to higher concentrations of redox species, it is possible to use redox mediators, which means that the main redox species do not flow with the electrolyte, which is restricted to the reservoirs. Instead, a redox mediator (secondary redox species) flows into the cell, reacts when in contact with the bipolar plate, and then goes back to the tank and reacts with the main redox species [5,266,275]. This principle is schematized in Figure 12. In order to circumvent the pressure drop issues due to higher concentrations of redox species, it is possible to use redox mediators, which means that the main redox species do not flow with the electrolyte, being restricted on the reservoirs. Instead, a redox mediator (secondary redox species) flows into the cell, reacts when in contact with the bipolar plate, and then goes back to the tank and reacts with the main redox species [5,266,275]. This principle is schematized in Figure 12. Therefore, it is possible to store energy on the main species while relying on the fluidity and viscosity of the redox mediator, not only decreasing the pressure drop but also enhancing the charge transport and thus the power output [266,271]. The major drawbacks of this approach is that since there are two kinetic processes involved (in cell and in tanks), the device electrochemical performance tends to decrease (coulombic and voltage efficiency, current/power density), despite there still being some divergence about this topic [53,276]. Additionally, this double kinetics system leads to a dependence between power and capacity [271,277] and the screening process of choosing mediator and active species gets even harder when compared to other electrolytes [271]. Figure 11. Organic slurry RFB based on all polymer particulate suspension reported by Yan et al. Figure 11. Organic slurry RFB based on all polymer particulate suspension reported by Yan et al. [274]. (a) Schematic [275]. (a) Schematic representation of the mentioned organic slurry RFB. (b) Illustration of the representation of the mentioned organic slurry RFB. (b) Illustration of the proposed kinetic mechanism to elucidate the proposed kinetic mechanism to elucidate the charge transfer particulates in the redox processes. (c) charge transfer particulates in the redox processes. (c) The capacity, coulombic efficiency, and voltage efficiency in a The capacity, coulombic efficiency, and voltage efficiency in a galvanostatic charge–discharge cycle galvanostatic charge–discharge cycle for current densities from 5 mA cm−2 to 20 mA cm−2. (d) Representation of the for current densities from 5 mA cm−2 to 20 mA cm−2. (d) Representation of the long-term stability long-term stability during charge–discharge cycles−2at 20 mA cm−2. (e) Representation of the polarization curves for different during charge–discharge cycles at 20 mA cm . (e) Representation of the polarization curves for different flowrates. Copyright 2019, Springer Nature. flowrates. Copyright 2019, Springer Nature.PDF Image | PNNL Vanadium Redox Flow Battery Stack
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