Wang Yi-Feng, Song Li-Na, Zheng Li-Jun, Wang Yue, Wu Jia-Yi, Xu Ji-Jing
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun, 130012, P. R. China.
International Center of Future Science, Jilin University, Changchun, 130012, P. R. China.
Angew Chem Int Ed Engl. 2024 Apr 22;63(17):e202400132. doi: 10.1002/anie.202400132. Epub 2024 Mar 15.
Li-CO batteries have received significant attention owing to their advantages of combining greenhouse gas utilization and energy storage. However, the high kinetic barrier between gaseous CO and the LiCO product leads to a low operating voltage (<2.5 V) and poor energy efficiency. In addition, the reversibility of LiCO has always been questioned owing to the introduction of more decomposition paths caused by its higher charging plateau. Here, a novel "trinity" Li-CO battery system was developed by synergizing CO, soluble redox mediator (2,2,6,6-tetramethylpiperidoxyl, as TEM RM), and reduced graphene oxide electrode to enable selective conversion of CO to LiCO. The designed Li-CO battery exhibited an output plateau reaching up to 2.97 V, higher than the equilibrium potential of 2.80 V for LiCO, and an ultrahigh round-trip efficiency of 97.1 %. The superior performance of Li-CO batteries is attributed to the TEM RM-mediated preferential growth mechanism of LiCO, which enhances the reaction kinetics and rechargeability. Such a unique design enables batteries to cope with sudden CO-deficient environments, which provides an avenue for the rationally design of CO conversion reactions and a feasible guide for next-generation Li-CO batteries.
锂-CO电池因其兼具温室气体利用和能量存储的优势而备受关注。然而，气态CO与LiCO产物之间的高动力学势垒导致其工作电压较低（<2.5 V）且能量效率不佳。此外，由于LiCO较高的充电平台引入了更多分解路径，其可逆性一直受到质疑。在此，通过协同CO、可溶性氧化还原介质（2,2,6,6-四甲基哌啶氧化物，即TEM RM）和还原氧化石墨烯电极，开发了一种新型的“三位一体”锂-CO电池系统，以实现CO向LiCO的选择性转化。所设计的锂-CO电池展现出高达2.97 V的输出平台，高于LiCO的2.80 V平衡电位，以及97.1%的超高往返效率。锂-CO电池的卓越性能归因于TEM RM介导的LiCO优先生长机制，该机制增强了反应动力学和可充电性。这种独特的设计使电池能够应对突发的CO缺乏环境，为合理设计CO转化反应提供了一条途径，并为下一代锂-CO电池提供了可行的指导。
