Technical bottlenecks of polyselenide shuttling and material volume variation significantly hamper the development of emerging sodium-selenium (Na-Se) batteries. The nanopore structure of substrate materials is demonstrated to play a vital role in stabilizing Se cathodes and approaching superior Na-ion storage properties. Herein, an ideal nanorod-like trimodal hierarchical porous carbon (THPC) host is fabricated through a facile one-step carbonization method for advanced Na-Se batteries. The THPC possesses a trimodal nanopore structure encompassing micropores, mesopores, and macropores, and functions as a good accommodator of Se molecules, a reservoir of polyselenide intermediates, a buffer for volume expansion of Se species during sodiation, and a promoter for electron/ion transfer in the electrochemical process. As a result, Na-Se batteries assembled with the Se-THPC composite cathode realize high utilization of Se, fast redox kinetics, and excellent cyclability. Furthermore, the Na-ion storage mechanism of the well-designed Se-THPC composite is profoundly revealed by in situ visual characterization techniques.
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