The lithium carbonate (Li2CO3)‐coated carbon microbead composites (LCO/CMB‐T) with the coating amount of 1.07, 2.88, and 7.39% are prepared by the impregnation process (IP). Three LCO/CMB‐T samples are first used in the piperidinium‐based hybrid electrolyte. It is found that the long charge–discharge cycles did not result in the decomposition or exfoliation of Li2CO3 coating. They can effectively prevent graphite electrode from exfoliation and suppress the graphite/electrolyte interfacial reaction. In three tested samples (IP‐1.07%, IP‐2.88% and IP‐7.39% for short), the IP‐2.88% sample showed the best cell performances and the highest capacity retention (82.9%) after 50 cycles. This work gives a new design method for the application of graphite materials in the ionic liquid‐based electrolyte. [ABSTRACT FROM AUTHOR]