Engineering the structure-directed functional properties of brominated organic additives for high-performance Li-CO2 batteries

In recent years, functional brominated organic additives in electrolytes have been widely studied during the CO2ER (CO2 evolution reaction) and CO2RR (CO2 reduction reaction) processes for Li-CO2 batteries. Due to their different structures, the functions of these additives are always unpredictable, multiple and limited. There seems to be a lot of materials to choose from for an additive, but there is no well-established and effective methodology to guide the selection. Herein, we introduced B3BPE, E4BCT and BPB into electrolytes for Li-CO2 batteries and focused on the structure-directed engineering of additives, including the position of halide substituent groups, the chain length of organic materials, their chain-break product as well as their corresponding difference in electrochemical properties, as additives for comparison. As a result, B3BPE has the longest chain length and strongest polarity. Experiments coupled with density functional theory simulations indicate that this structure exhibits the stronger interaction with Li2CO3, which benefits the CO2ER process, the charging voltage can be maintained at 3.90 V for 120 cycles even with a Super P cathode. In this work, we provided an electrolyte-selection engineering for brominated organic compounds, further inspiring in-depth understanding for bromide additives in future high-performance Li-CO2 batteries.