DABCOnium: Ein effizienter und Hochspannungs‐stabiler Singulett‐Sauerstoff‐Löscher für Metall‐O₂‐Zellen

Abstract

Singulett-Sauerstoff ( 1 O 2 )verursacht einen Großteil der parasitären Chemie während des Zellbetriebs von nichtwässrigen Alkalimetall-O 2 -Batterien und trägt auchz ur Grenzflächenreaktivitätv on Übergangsmetalloxid-Einlagerungsverbindungen bei. Wirf ühren DABCOnium, die monoalkylierte Form von 1,4-Diazabicyclo[2.2.2]octan (DABCO), als effizienten 1 O 2 -Lçscher mit ungewçhnlichh oher Oxidationsstabilitätvon % 4.2 Vv s. Li/Li + ein. Bisher bekannte Lçschers ind stark Lewis-basische Amine mit zu geringer Oxidationsstabilität. DABCOnium ist eine ionische Flüssigkeit, nicht flüchtig, im Elektrolyten hochlçslich,s tabil gegen Superoxid und Peroxid, und kompatibel mit Lithiummetall. Die elektrochemische Stabilitätd ecktd en erforderlichen Be-reichfürMetall-O 2 -Batterien ab und reduziert die 1 O 2 -bedingte parasitäre Chemie erheblich, wie fürd ie Li-O 2 -Zelle gezeigt wird.

Pathways to Triplet or Singlet Oxygen during the Dissociation of Alkali Metal Superoxides: Insights by Multireference Calculations of Molecular Model Systems

“…Second, the manipulation of the crossing points by, for example, taking advantage of spin–orbit coupling effects by introducing heavy elements may be an option to avoid singlet‐oxygen formation by creating avoided crossings (see Figure ). These suggestions go beyond the recently addressed use of quenching agents in the electrolyte of metal/oxygen batteries, which are aimed at deactivating the highly reactive singlet‐oxygen species during battery cycling. Our study can help to shape further research studies shedding light on how to prevent the formation of singlet oxygen in the first place, and ultimately help to minimize the deleterious influence of unwanted side reactions in aprotic metal/oxygen batteries.…”

Understanding the Transport of Atmospheric Gases in Liquid Electrolytes for Lithium–Air Batteries

“…redox mediators or SEI-forming additives, etc). 13,[16][17][18][19][20][21][22][23] The current density that can be achieved during discharge also depends on the electrolyte and is determined by the concentration c O2 and the diffusion coefficient D O2 of oxygen. The mass transport limiting current I lim can be calculated from…”

An Efficient and Reversible Singlet Oxygen Quencher for Suppressing Photobleaching of Organic Fluorescent Dyes

“…Synthesis of DABCOnium : DABCOnium was synthesized according to the literature with proper modifications [23] . Briefly, 2 g (17.84 mmol) of diazabicyclo[2.2.2]octane was dissolved in 20 mL acetonitrile to form a colorless solution.…”

“…In the former case, the quencher, which is normally reductant, reacts irreversibly with singlet oxygen, and produces new products. This approach is highly efficient as the quencher reacts rapidly with singlet oxygen [20–23] . However, the quencher is constantly consumed during the process, and the formed products will accumulate and put potentially disturbance to normal biological activities.…”

“…Unfortunately, they found that the modification of DABCO completely lost their ability to quench singlet oxygen. Very recently, Petit and coworkers made a breakthrough by synthesizing a mono‐alkylated derivative of DABCO, DABCOnium, and found the derivative can efficiently and reversibly quench singlet oxygen in batteries, and is non‐volatile at room temperature [23] . The synthesized DABCOnium had a high oxidative stability over high voltages, and had been successfully used for suppressing singlet oxygen generation in metal‐oxygen batteries.…”