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Updated: May 23, 2025

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Facet-Controlled NaO2 Crystal Growth via Microporosity Modulation in Commercial Carbon Air Cathodes for Sodium-Oxygen
Arantzazu Letona-Elizburu1,2, Jhony Xavier Flores-Lasluisa1, Mireia Martín-Marcianes1,3
1Center for Cooperative Research on Alternative Energies (CIC energiGUNE), Basque Research and Technology Alliance (BRTA), Alava Technology Park, Albert Einstein 48, 01510 Vitoria-Gasteiz, Spain.
Abstract:
Aprotic sodium-oxygen batteries (Na-O2) are promising high-capacity energy storage devices, where the electrodeposition of sodium superoxide (NaO2) on a carbon-based air cathode can theoretically achieve an energy density of 1086 Wh kg-1. This study demonstrates the significant influence of micropores in commercial graphene nanoplatelets (GNPs) on the nucleation and growth of NaO2. The findings reveal that micropores could promote anisotropic interactions with reduced oxygen species formed during discharge. Adsorption-induced confinement of oxygen or superoxide species within the micropores facilitates preferential growth along specific crystallographic orientations, leading to the formation of 2D plate-like structures. This behavior contrasts with the isotropic 3D cubic forms typically observed on nonporous or mesoporous substrates. In GNPs with a medium surface area (300 m2 g-1), a certain contribution of anisotropic growth can reduce cycling hysteresis and enhance Coulombic efficiency of the cell. Understanding the relationship among the microporous architecture of carbon cathodes, NaO2 growth dynamics, and facet control is crucial for optimizing the efficiency and durability of Na-O2 batteries.
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