Aprotic lithium-oxygen (Li-O2 ) batteries have attracted considerable attention in recent years owing to their outstanding theoretical energy density. A major challenge is their poor reversibility caused by degradation reactions, which mainly occur during battery charge and are still poorly understood. Herein, we show that singlet oxygen ((1) Δg ) is formed upon Li2 O2 oxidation at potentials above 3.5 V. Singlet oxygen was detected through a reaction with a spin trap to form a stable radical that was observed by time- and voltage-resolved in operando EPR spectroscopy in a purpose-built spectroelectrochemical cell. According to our estimate, a lower limit of approximately 0.5 % of the evolved oxygen is singlet oxygen. The occurrence of highly reactive singlet oxygen might be the long-overlooked missing link in the understanding of the electrolyte degradation and carbon corrosion reactions that occur during the charging of Li-O2 cells.
Time-resolved formation of micro-structured mossy/dendritic lithium is investigated during battery cycling byoperandoEPR spectroscopy, using a novel electrochemical cell design.
The formation of nanoscale zinc oxide particles with an almost-monomodal size distribution synthesized by microwave heating of solutions of mononuclear zinc oximato or zinc acetylacetonato complexes in various alkoxyethanols is investigated. Transparent stable suspensions that contain these particles can be obtained from the zinc oximato precursor. Based on electron paramagnetic resonance (EPR) studies, a core/shell model with a finite surface shell thickness of 1.000 ± 0.025 nm is proposed for the ZnO nanoparticles. Field-effect transistor (FET) devices with these ZnO particles as the active semiconducting layer exhibited a charge carrier mobility of 0.045 cm2/(V s) and I
on/off current ratios of ∼460.000, with a threshold voltage of 8.78 V.
Aprotic lithium-oxygen (Li-O 2 )b atteries have attracted considerable attention in recent years owing to their outstanding theoretical energy density.Am ajor challenge is their poor reversibility caused by degradation reactions,which mainly occur during battery charge and are still poorly understood. Herein, we showt hat singlet oxygen ( 1 D g )i s formed upon Li 2 O 2 oxidation at potentials above 3.5 V. Singlet oxygen was detected through areaction with aspin trap to form as table radical that was observed by time-and voltageresolved in operando EPR spectroscopyi nap urpose-built spectroelectrochemical cell. According to our estimate,alower limit of approximately 0.5 %o ft he evolved oxygen is singlet oxygen. The occurrence of highly reactive singlet oxygen might be the long-overlooked missing link in the understanding of the electrolyte degradation and carbon corrosion reactions that occur during the charging of Li-O 2 cells.
The degradation of LiNi0.8Co0.15Al0.05O2 (LNCAO) is reflected by the electrochemical performance in the fatigued state and correlated with the redox behavior of these cathodes. The detailed electrochemical performance of these samples is investigated by galvanostatic and voltammetric cycling as well as with the galvanostatic intermittent titration technique (GITT). Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy was used to investigate the oxidation state of all three materials at the Ni L2,3, O K, and Co L2,3 edges at five different states of charge. Surface and more bulklike properties are distinguished by total electron yield (TEY) and fluorescence yield (FY) measurements. The electrochemical investigations revealed that the changes in the cell performance of the differently aged materials can be explained by considering the reaction kinetics of the intercalation/deintercalation process. The failure of the redox process of oxygen and nickel at low voltages leads to a significant decrease of the reaction rates in the fatigued cathodes. The accompanied cyclic voltammogram (CV) peaks appear as two peaks because of the local minimum of the reaction rate, although it is one peak in the CV of the calendarically aged LNCAO. The absence of the oxidation/reduction process at low voltages can be traced back to changes in the surface morphology (formation of a NiO-like structure). Further consequences of these material changes are overpotentials, which lead to capacity losses of up to 30% (cycled with a C/3 rate).
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