Enhancing the process of CO2 reduction reaction by using CTAB to construct contact ion pair in Li-CO2 battery

Aprotic Li-CO2 batteries have attracted growing interest due to their high theoretical energy density and its ability to use green house gas CO2 for energy storage. However, the poor ability of activating CO2 in organic electrolyte often leads to the premature termination of CO2 reduction reaction (CO2RR) directly. Here in this work, cetyl trimethyl ammonium bromide (CTAB) was introduced into a dimethyl sulfoxide (DMSO) based Li-CO2 battery for the first time to enhance the CO2RR. Significantly improved electrochemical performances, including reduced discharge over-potential and increased discharge capacity, can be achieved with the addition of CTAB. Ab initio molecular dynamics (AIMD) simulations show that quaternary ammonium group CTA+ can accelerate CO2 reduction process by forming more stable contact ion pair (CIP) with CO2–, reducing the energy barrier for CO2RR, thus improving the CO2 reduction process. In addition, adding CTA+ is also favorable for the solution-phase growth of discharge products because of the improved migration ability of stable CTA+-CO2– CIP in the electrolyte, which is beneficial for improving the utilization ratio of cathode. This work could facilitate the development of CO2RR by providing a novel understanding of CO2RR mechanism in organic system. A cation additive of CTA+can accelerate the CO2 reduction chemistry in Li-CO2 battery by forming stable contact ion pair with CO2– [CTA+-CO2– contact ion pair (CIP)] and reducing the energy barrier for CO2 reduction reaction (CO2RR). The CTA+-CO2– CIP can optimize the reaction path of the battery and makes the discharge products more easily formed in electrolyte, which is beneficial for improving the utilization rate of the cathode and thus increase the capacity of the Li-CO2 battery. [Display omitted]