The production of Li2CO3/C through CO2 reduction reaction in nonaqueous systems is a complex four‐electron, multi‐step process, and the short existence time of intermediate monomers is not conducive to observation, which causes great difficulties in clarifying and regulating the CO2 reduction path. Herein, ferrocene (Fc) as a functional additive into the electrolyte can stabilize the discharge intermediates and favor the occurrence of the two‐electron reaction path during CO2RR, which leads to more stable operation of the Li‐CO2 battery; with the assistance of Fc, the CO2 reduction pathway in Li‐CO2 battery is also clarified. Theoretical calculation analysis combined with experimental characterization observation confirms that Fc can shorten the CO2 reduction distance through interaction with CO2 and affecting the solvent environment around Li+, stabilize intermediate products to clarify the discharge path. The existence time of intermediates and discharge depth of the battery are key factors affecting the CO2 reduction pathway. The Li2C2O4 formed by CO2 reduction through the 2‐electron pathway is more favorable for the reversible operation of the Li‐CO2 battery than Li2CO3/C through the 4‐electron pathway. This work provides inspiration for clarifying the reaction mechanism and regulating the CO2 reduction pathway to improve the electrochemical performance of Li‐CO2 battery in the future.

中文翻译：

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调整 CO2 电催化还原路径以实现高性能 Li-CO2 电池


非水体系中CO2还原反应生产Li2CO3/C是一个复杂的四电子、多步过程，且中间单体存在时间短不利于观察，这给阐明和调控CO2还原过程带来了很大困难小路。其中，二茂铁（Fc）作为电解液中的功能添加剂可以稳定放电中间体，有利于CO2RR过程中双电子反应路径的发生，从而使Li-CO2电池运行更加稳定；在Fc的帮助下，Li-CO2电池中的CO2还原途径也被阐明。理论计算分析结合实验表征观察证实，Fc可以通过与CO2相互作用并影响Li+周围的溶剂环境来缩短CO2还原距离，稳定中间产物以澄清放电路径。中间体的存在时间和电池的放电深度是影响CO2还原途径的关键因素。通过2电子途径还原CO2形成的Li2C2O4比通过4电子途径还原Li2CO3/C更有利于Li-CO2电池的可逆运行。这项工作为阐明反应机理和调控CO2还原途径以提高未来Li-CO2电池的电化学性能提供了启发。