Renewable power sources have drawn interest due to scarcity of fossil fuels and associated pollution during their combustion-based power production. Renewables are projected to produce approximately 60% of US electricity generation by 2050, with an expected contribution of 2000 TW-h from wind power alone. To overcome the mismatch between electricity demand and intermittent supply, such power plants require large-scale energy-storage device integrated with them. In contrast to other technologies, redox flow batteries (RFBs) offer independently scalable power and energy capacity that is demanded for such applications. Despite significant achievement in their designs through experimentation and modeling, limited understanding has been established to date concerning their transient response while operating under irregular charge/discharge scenarios in renewable-powered grids and micro-grids. Under such conditions pore-scale mass transport physics and different mechanisms of concentration polarization can occur, but the conventional film law of mass transfer (FLoMT) using a constant Sherwood number cannot capture time-varying diffusion layer thickness near electrode surfaces. Further, the mean solute advection rate through porous RFB electrodes can deviate from the value expected from product of superficial velocity and average concentration inside the electrode if pore-scale concentration polarization is substantial. Consideration of these effects in the present bottom-up theory makes it applicable to over-limiting conditions, while predicting concentration polarization in agreement with experimental observations. We accomplish this by creating theory with similarity to the theory of Ralph White and co-workers for solid-state, particle-scale diffusion in Li-ion batteries [J. Power Sources, 2012, Vols. 214 and 218], while our theory is instead applied to an arbitrary representative volume element of flowing liquid electrolyte inside electrode pores.Here, we present a theory to incorporate these transient effects into a bottom-up transient model (B-UTM) by using frequency-dependent transfer functions (TFs) that are derived from the Fourier transformed pore-scale mass conservation equations (MCEs). These TFs preserve pore-scale mass transfer physics during their embedding into an up-scaled model. One of these TFs is the spectral Sherwood number that extends the film law of mass transfer to transient conditions and that correlates reactive flux with concentration polarization through an output-input relationship in the frequency domain. Another TF named the advective-flux transfer function captures the acceleration/suppression of solute advection rate that arises from the inhomogeneity in pore-scale concentration distributions. We first present validation of this theory using transient RFB experiments where the introduced B-UTM predicts the time evolution of concentration polarization in good agreement. Meanwhile the conventional FLoMT model that uses time-independent Sherwood number and neglects the solute acceleration/suppression effect shows systematically larger polarization (up to 400%), which restricts such models from simulating charging/discharging with applied current near and above the limiting current.The utility of the introduced bottom-up theory is demonstrated by incorporating it into a multi-scale RFB model in which redox-active electrolyte flows through a porous electrode comprised of an array of circular cylinders in crossflow that mimics commonly used carbon felt. The frequency dependence of the introduced TFs obtained from numerical solution of pore-scale MCEs are analyzed for different electrode porosity and Péclet number, where both the TFs reach a non-zero finite value in the limit of vanishing frequency. The non-zero value of the spectral Sherwood number in this limit is identical to the Sherwood number obtained in the pseudo-steady limit (PSL) where transient effects are negligible. With increasing frequency both the TFs show a transition from lagless response to semi-infinite Warburg response with orders higher values compared to that of the PSL. Finally, these TFs are embedded into an up-scaled model to obtain the time-domain response of RFBs operating under a step impulse applied current with different step durations. Numerically obtained concentration polarization and the average reactant concentration inside electrodes is used to construct non-dimensional regime maps showing a regime of over-limiting current. The results show that fast current fluctuations are sustained even when current exceeds the limiting current, which provides a means to increase the utilization of charge capacity of existing flow-based electrochemical devices that are operated under transient conditions. The theory introduced here can find applicability in other flow-based electrochemical devices including electrochemical separations and CO2 capture. Figure 1