Poly(vinylidene fluoride) (PVDF) Binder Degradation in Li–O ₂ Batteries: A Consideration for the Characterization of Lithium Superoxide

We show that a common Li–O2 battery cathode binder, poly(vinylidene fluoride) (PVDF), degrades in the presence of reduced oxygen species during Li–O2 discharge when adventitious impurities are present. This degradation process forms products that exhibit Raman shifts (∼1133 and 1525 cm–1) nearly identical to those reported to belong to lithium superoxide (LiO2), complicating the identification of LiO2 in Li–O2 batteries. We show that these peaks are not observed when characterizing extracted discharged cathodes that employ poly(tetrafluoroethylene) (PTFE) as a binder, even when used to bind iridium-decorated reduced graphene oxide (Ir-rGO)-based cathodes similar to those that reportedly stabilize bulk LiO2 formation. We confirm that for all extracted discharged cathodes on which the 1133 and 1525 cm–1 Raman shifts are observed, only a 2.0 e–/O2 process is identified during the discharge, and lithium peroxide (Li2O2) is predominantly formed (along with typical parasitic side product formation). Our results strongly suggest that bulk, stable LiO2 formation via the 1 e–/O2 process is not an active discharge reaction in Li–O2 batteries.