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J Phys Chem Lett. 2015 Apr 2;6(7):1254-9. doi: 10.1021/acs.jpclett.5b00324. Epub 2015 Mar 23.

Trade-Offs in Capacity and Rechargeability in Nonaqueous Li-O2 Batteries: Solution-Driven Growth versus Nucleophilic Stability.

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†Institute for Combustion Technology, RWTH, Templergraben 64, Aachen 52056, Germany.
§Department of Mechanical Engineering, Carnegie Mellon University, 5000 Forbes Avenue, Pittsburgh, Pennsylvania 15213, United States.
‡SUNCAT, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025-7015, United States.


The development of high-capacity rechargeable Li-O2 batteries requires the identification of stable solvents that can promote a solution-based discharge mechanism, which has been shown to result in higher discharge capacities. Solution-driven discharge product growth requires dissolution of the adsorbed intermediate LiO2*, thus generating solvated Li+ and O2(-) ions. Such a mechanism is possible in solvents with high Gutmann donor or acceptor numbers. However, O2(-) is a strong nucleophile and is known to attack solvents via proton/hydrogen abstraction or substitution. This kind of a parasitic process is extremely detrimental to the battery's rechargeability. In this work, we develop a thermodynamic model to describe these two effects and demonstrate an anticorrelation between solvents’ stability and their ability to enhance capacity via solution-mediated discharge product growth. We analyze the commonly used solvents in the same framework and describe why solvents that can promote higher discharge capacity are also prone to degradation. Solvating additives for practical Li-O2 batteries will have to be outliers to this observed anticorrelation.


additive engineering; lithium−air solution process; nucleophilic attack; solvent stability

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