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Lithium–air batteries possess ultrahigh energy density compared to lithium-ion batteries because oxygen is applied as the reacting matter of the cathode without restrictions. However, they cannot be applied at present, owing to their semiopen systems that result in water intrusion and electrolyte evaporation. Herein, we loaded modified silver nanoparticles on the carbon paper of the cathode to construct micro–nano hierarchical structures which exhibited superhydrophobicity and oleophobicity, preventing water entry and electrolyte volatilization. Thereby, the cycle life of the battery was increased. The batteries with modified carbon paper exhibited remarkable cycling performance in different environments, such as pure oxygen (over 800 h), humid oxygen (∼30% RH, over 1200 h), and ambient air (∼50% RH, over 450 h). The maximum discharge specific capacity reached 9325.8 and 11 787 mAh g–1 at a current density of 100 mA g–1 in humid oxygen and ambient air, respectively.

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