Upgrading Cycling Stability and Capability of Hybrid Na‐CO2 Batteries via Tailoring Reaction Environment for Efficient Conversion CO2 to HCOOH.

Rechargeable Na‐CO2 batteries are considered to be an effective way to address the energy crisis and greenhouse effect due to their dual functions of CO2 fixation/utilization and energy storage. However, the insolubility and irreversibility of solid discharge products lead to poor discharge capacity and poor cycle performance. Herein, a novel strategy is proposed to enhance the electrochemical performance of hybrid Na‐CO2 batteries, using water‐in‐salt electrolyte (WiSE) to establish an optimal reaction environment, regulate the CO2 reduction pathway, and ultimately convert the discharge product of the battery from Na2CO3 to formic acid (HCOOH). This strategy effectively resolves the issue of poor reversibility, allowing the battery to exhibit excellent cycle performance (over 1200 cycles at 30 °C), especially under low‐temperature conditions (2534 cycles at −20 °C). Furthermore, density functional theory (DFT) calculations and experiments indicate that by adjusting the relative concentration of H/O atoms at the electrolyte/catalyst interface, the CO2 reduction pathway in the battery can be regulated, thus effectively enhancing CO2 capture capability and consequently achieving an ultra‐high discharge specific capacity of 148.1 mAh cm−2. This work effectively promotes the practical application of hybrid Na‐CO2 batteries and shall provide a guidance for converting CO2 into products with high‐value‐added chemicals. [ABSTRACT FROM AUTHOR]