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Brunini, VE

Publications and source records attributed to Brunini, VE.

Electroactive-Zone Extension in Flow-Battery Stacks

Flowable suspensions that conduct both electrons and ions can enable the use of energy-dense electroactive species in flow batteries [M. Duduta et al., Adv. Energy Mater., 1, 511 (2011); Z. Li et al., Phys. Chem. Chem. Phys., 15, 15,833 (2013); F. Fan et al., Nano Lett., 14, 2210 (2014)]. In comparison with conventional flow batteries where electrochemical reactions are confined to a fixed current-collector region, electronically conductive flow electrodes permit electrochemical reactions to extend outside of the physical confines of the stack. We have measured and modeled how mixed-conduction enables an electroactive zone (EAZ, in which electrochemical reactions occur) that is of greater spatial extent than current collectors, the extension being termed side zone, SZ. Electrochemical reactions in SZs can reduce coulombic and energetic efficiency. Here we show that for realistic suspension properties and operating conditions, the added inefficiency is small in practice, and can be further mitigated by using appropriate operating conditions and/or materials choices. For the specific example of a non-aqueous Li4Ti5O12 suspension, we show that EAZ extension contributes less than 1% additional efficiency loss at C/10 rates for current collectors greater than 20 mm long. (C) 2014 Elsevier Ltd. All rights reserved.

Smith, KC↗

Modeling the hydrodynamic and electrochemical efficiency of semi-solid flow batteries

A mathematical model of flow cell operation incorporating hydrodynamic and electrochemical effects in three dimensions is developed. The model and resulting simulations apply to recently demonstrated high energy-density semi-solid flow cells. In particular, state of charge gradients that develop during low flow rate operation and their effects on the spatial non-uniformity of current density within flow cells are quantified. A one-dimensional scaling model is also developed and compared to the full three-dimensional simulation. The models are used to demonstrate the impact of the choice of electrochemical couple on flow cell performance. For semi-solid flow electrodes, which can use solid active materials with a wide variety of voltage-capacity responses, we find that cell efficiency is maximized for electrochemical couples that have a relatively flat voltage vs. capacity curve, operated under slow flow conditions. For example, in flow electrodes limited by macroscopic charge transport, an LiFePO4-based system requires one-third the polarization to reach the same cycling rate as an LiCoO2-based system, all else being equal. Our conclusions are generally applicable to high energy density flow battery systems, in which flow rates can be comparatively low for a given required power. (C) 2012 Elsevier Ltd. All rights reserved.

Brunini, VE↗