Understanding capacity fade in organic redox-flow batteries by combining spectroscopy with statistical inference techniques.

Organic redox-active molecules are attractive as redox-flow battery (RFB) reactants because of their low anticipated costs and widely tunable properties. Unfortunately, many lab-scale flow cells experience rapid material degradation (from chemical and electrochemical decay mechanisms) and capacity fade during cycling (>0.1%/day) hindering their commercial deployment. In this work, we combine ultraviolet-visible spectrophotometry and statistical inference techniques to elucidate the Michael attack decay mechanism for 4,5-dihydroxy-1,3-benzenedisulfonic acid (BQDS), a once-promising positive electrolyte reactant for aqueous organic redox-flow batteries. We use Bayesian inference and multivariate curve resolution on the spectroscopic data to derive uncertainty-quantified reaction orders and rates for Michael attack, estimate the spectra of intermediate species and establish a quantitative connection between molecular decay and capacity fade. Our work illustrates the promise of using statistical inference to elucidate chemical and electrochemical mechanisms of capacity fade in organic redox-flow battery together with uncertainty quantification, in flow cell-based electrochemical systems.

Unveiling the Cerium(III)/(IV) Structures and Charge-Transfer Mechanism in Sulfuric Acid.

The Ce3+/Ce4+ redox couple has a charge transfer (CT) with extreme asymmetry and a large shift in redox potential depending on electrolyte composition. The redox potential shift and CT behavior are difficult to understand because neither the cerium structures nor the CT mechanism are well understood, limiting efforts to improve the Ce3+/Ce4+ redox kinetics in applications such as energy storage. Herein, we identify the Ce3+ and Ce4+ structures and CT mechanism in sulfuric acid via extended X-ray absorption fine structure spectroscopy (EXAFS), kinetic measurements, and density functional theory (DFT) calculations. We show EXAFS evidence that confirms that Ce3+ is coordinated by nine water molecules and suggests that Ce4+ is complexed by water and three bisulfates in sulfuric acid. Despite the change in complexation within the first coordination shell between Ce3+ and Ce4+, we show that the kinetics are independent of the electrode, suggesting outer-sphere electron-transfer behavior. We identify a two-step mechanism where Ce4+ exchanges the bisulfate anions with water in a chemical step followed by a rate-determining electron transfer step that follows Marcus theory (MT). This mechanism is consistent with all experimentally observed structural and kinetic data. The asymmetry of the Ce3+/Ce4+ CT and the observed shift in the redox potential with acid is explained by the addition of the chemical step in the CT mechanism. The fitted parameters from this rate law qualitatively agree with DFT-predicted free energies and the reorganization energy. The combination of a two-step mechanism with MT should be considered for other metal ion CT reactions whose kinetics have not been appropriately described.