Operando detection and suppression of spurious singlet oxygen in Li-O₂ batteries

The rechargeable lithium air (oxygen) battery (Li-O-2) has very high energy density, comparable to that of fossil fuels (similar to 3600 W h kg(-1)). However, the parasitic reactions of the O-2 reduction products with solvent and electrolyte lead to capacity fading and poor cyclability. During the oxygen reduction reaction (ORR) in aprotic solvents, the superoxide radical anion (O(2)c-) is the main one-electron reaction product, which in the presence of Li+ ions undergoes disproportionation to yield Li2O2 and O-2, a fraction of which results in singlet oxygen (O-1(2)). The very reactive O-1(2) is responsible for the spurious reactions that lead to high charging overpotential and short cycle life due to solvent and electrolyte degradation. Several techniques have been used for the detection and suppression of O-1(2) inside a Li-O-2 battery under operation and to test the efficiency and electrochemical stability of different physical quenchers of O-1(2): azide anions, 1,4-diazabicyclo[2.2.2]octane (DABCO) and triphenylamine (TPA) in different solvents (dimethyl sulfoxide (DMSO), diglyme and tetraglyme). Operando detection of O-1(2) inside the battery was accomplished by following dimethylanthracene fluorescence quenching using a bifurcated optical fiber in front-face mode through a quartz window in the battery. Differential oxygen-pressure measurements during charge-discharge cycles vs. charge during battery operation showed that the number of electrons per oxygen molecule was n > 2 in the absence of physical quenchers of O-1(2), due to spurious reactions, and n = 2 in the presence of physical quenchers of O-1(2), proving the suppression of spurious reactions. Battery cycling at a limited specific capacity of 500 mA h gC(-1) for the MWCNT cathode and 250 mA gC(-1) current density, in the absence and presence of a physical quencher or a physical quencher plus the redox mediator I-3(-)/I- (with a lithiated Nafion (R) membrane), showed increasing cyclability according to coulombic efficiency and cell voltage data over 100 cycles. Operando Raman studies with a quartz window at the bottom of the battery allowed detection of Li2O2 and excess I-3(-) redox mediator during discharge and charge, respectively.