Lithium bis(trifluoromethanesulfonyl)imide, commonly known as LiTFSI, and its analogs, are critical electrolytes for lithium batteries and solar cells. However, the commercialization of LiTFSI through thermal chemical synthesis relies on the use of NH3 intermediates, which involves multiple catalytic and purification processes, leading to substantial carbon emissions. Therefore, developing a method for the direct synthesis of LiTFSI from N2 under mild conditions becomes particularly important.