ABSTRACT
We have synthesized a library of perovskite oxides with the composition La1- xSr xBO3-δ ( x = 0-1; B = Fe, Mn, Co) to systematically study anion-based pseudocapacitance. The electrochemical capacitance of these materials was evaluated by cyclic voltammetry and galvanostatic charging/discharging in 1 M KOH. We find that greater oxygen vacancy content (δ) upon systematic incorporation of Sr2+ linearly increases the surface-normalized capacity with a slope controlled by the B-site element. La0.2Sr0.8MnO2.7 exhibited the highest specific capacitance of 492 F g-1 at 5 mV s-1 relative to the Fe and Co oxides. In addition, the first all-perovskite asymmetric pseudocapacitor has been successfully constructed and characterized in neutral and alkaline aqueous electrolytes. We demonstrate that the asymmetric pseudocapacitor cell voltage can be increased by widening the difference between the B-site transition metal redox potentials in each electrode resulting in a maximum voltage window of 2.0 V in 1 M KOH. Among the three pairs of asymmetric pseudocapacitors constructed from SrCoO2.7, La0.2Sr0.8MnO2.7, and brownmillerite (BM)-Sr2Fe2O5, the BM-Sr2Fe2O5//SrCoO2.7 combination performed the best with a high energy density of 31 Wh kg-1 at 450 W kg-1 and power density of 10 000 W kg-1 at 28 Wh kg-1.
ABSTRACT
Perovskite oxides are active room-temperature bifunctional oxygen electrocatalysts in alkaline media, capable of performing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with lower combined overpotentials relative to their precious metal counterparts. However, their semiconducting nature necessitates the use of activated carbons as conductive supports to generate applicably relevant current densities. In efforts to advance the performance and theory of oxide electrocatalysts, the chemical and physical properties of the oxide material often take precedence over contributions from the conductive additive. In this work, we find that carbon plays an important synergistic role in improving the performance of La1-xSrxCoO3-δ (0 ≤ x ≤ 1) electrocatalysts through the activation of O2 and spillover of radical oxygen intermediates, HO2- and O2-, which is further reduced through chemical decomposition of HO2- on the perovskite surface. Through a combination of thin-film rotating disk electrochemical characterization of the hydrogen peroxide intermediate reactions (hydrogen peroxide reduction reaction (HPRR), hydrogen peroxide oxidation reaction (HPOR)) and oxygen reduction reaction (ORR), surface chemical analysis, HR-TEM, and microkinetic modeling on La1-xSrxCoO3-δ (0 ≤ x ≤ 1)/carbon (with nitrogen and non-nitrogen doped carbons) composite electrocatalysts, we deconvolute the mechanistic aspects and contributions to reactivity of the oxide and carbon support.
ABSTRACT
We investigate the source of Raman background signal commonly misidentified as fluorescence in nonaqueous electrolytes via a variety of spectroscopies (Raman, fluorescence, NMR) and find evidence of hydrogen-bonding interactions. This hydrogen bonding gives rise to broadband anharmonic vibrational modes and suggests that anions play an important and underappreciated role in the structure of nonaqueous electrolytes. Controlling electrolyte structure has important applications in advancing in operando spectroscopy measurements as well as understanding the stability of high concentration electrolytes for next-generation electrochemical energy storage devices.
