Abstract

AbstractThe severe performance degradation of high‐capacity Li−O2 batteries induced by Li dendrite growth and concentration polarization from the low Li+ transfer number of conventional electrolytes hinder their practical applications. Herein, lithiated Nafion (LN) with the sulfonic group immobilized on the perfluorinated backbone has been designed as a soluble lithium salt for preparing a less flammable polyelectrolyte solution, which not only simultaneously achieves a high Li+ transfer number (0.84) and conductivity (2.5 mS cm−1), but also the perfluorinated anion of LN produces a LiF‐rich SEI for protecting the Li anode from dendrite growth. Thus, the Li−O2 battery with a LN‐based electrolyte achieves an all‐round performance improvement, like low charge overpotential (0.18 V), large discharge capacity (9508 mAh g−1), and excellent cycling performance (225 cycles). Besides, the fabricated pouch‐type Li–air cells exhibit promising applications to power electronic equipment with satisfactory safety.

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