Amphi-Active Superoxide-Solvating Charge Redox Mediator for Highly Stable Lithium-Oxygen Batteries.

A multifunctional electrolyte additive for lithium oxygen batteries (LOBs) was designed to have (1) a redox-active moiety to mediate decomposition of lithium peroxide (Li2O2 as the final discharge product) during charging and (2) a solvent moiety to solvate and stabilize lithium superoxide (LiO2 as the intermediate discharge product) in electrolyte during discharging. 4-Acetamido-TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidin-1-yl)oxyl) or AAT was employed as the additive working for both charge and discharge processes (amphi-active). The redox-active moiety was rooted in TEMPO, while the acetamido (AA) functional group inherited the high donor number (DN) of N,N-dimethylacetamide (DMAc). Integrating two functional moieties (TEMPO and AA) into a single molecule resulted in the bifunctionality of AAT (1) facilitating Li2O2 decomposition by the TEMPO moiety and (2) encouraging the solvent mechanism of Li2O2 formation by the high-DN AA moiety. Significantly improved LOB performances were achieved by the superoxide-solvating charge redox mediator, which were not obtained by a simple cocktail of TEMPO and DMAc.

Shifting Target Reaction from Oxygen Reduction to Superoxide Disproportionation by Tuning Isomeric Configuration of Quinone Derivative as Redox Mediator for Lithium-Oxygen Batteries.

Quinones having a fully conjugated cyclic dione structure have been used as redox mediators in electrochemistry. 2,5-Ditert-butyl-1,4-benzoquinone (DBBQ or DB-p-BQ) as a para-quinone derivative is one of the representative discharge redox mediators for facilitating the oxygen reduction reaction (ORR) kinetics in lithium-oxygen batteries (LOBs). Herein, we presented that the redox activity of DB-p-BQ for electron mediation was possibly used for facilitating superoxide disproportionation reaction (SODR) by tuning the isomeric configuration of the carbonyl groups of the substituted quinone to change its reduction potentials. First, we expected a molecule having its reduction potential between oxygen/superoxide at 2.75 V versus Li/Li+ and superoxide/peroxide at 3.17 V to play a role of the SODR catalyst by transferring an electron from one superoxide (O2-) to another superoxide to generate dioxygen (O2) and peroxide (O22-). By changing the isomeric configuration from para (DB-p-BQ) to ortho (DB-o-BQ), the reduction potential of the first electron transfer (Q/Q-) of the ditert-butyl benzoquinone shifted positively to the potential range of the SODR catalyst. The electrocatalytic SODR-promoting functionality of DB-o-BQ kept the reactive superoxide concentration below a harmful level to suppress superoxide-triggered side reaction, improving the cycling durability of LOBs, which was not achieved by the para form. The second electron transfer process (Q-/ Q2-) of the DB-o-BQ, even if the same process of the para form was not used for facilitating ORR, played a role of mediating electrons between electrode and oxygen like the Q/Q- process of the para form. The ORR-promoting functionality of the ortho form increased the LOB discharge capacity and reduced the ORR overpotential.

Critical Void Dimension of Carbon Frameworks to Accommodate Insoluble Products of Lithium-Oxygen Batteries.

High-energy density lithium-oxygen batteries (LOBs) seriously suffer from poor rate capability and cyclability due to the slow oxygen-related electrochemistry and uncontrollable formation of lithium peroxide (Li2O2) as an insoluble discharge product. In this work, we accommodated the discharge product in macro-scale voids of a carbon-framed architecture with meso-dimensional channels on the carbon frame and open holes connecting the neighboring voids. More importantly, we found that a specific dimension of the voids guaranteed high capacity and cycling durability of LOBs. The best LOB performances were achieved by employing the carbon-framed architecture having voids of 0.8 µm size as the cathode of the LOB when compared with the cathodes having voids of 0.3 and 1.4 µm size. The optimized void size of 0.8 µm allowed only a monolithic integrity of lithium peroxide deposit within a void during discharging. The deposit was grown to be a yarn ball-looking sphere exactly fitting the shape and size of the void. The good electric contact allowed the discharge product to be completely decomposed during charging. On the other hand, the void space was not fully utilized due to the mass transfer pathway blockage at the sub-optimized 0.3 µm and the formation of multiple deposit integrities within a void at the sur-optimized 1.4 µm. Consequently, the critical void dimension at 0.8 µm was superior to other dimensions in terms of the void space utilization efficiency and the lithium peroxide decomposition efficiency, disallowing empty space and side reactions during discharging.