Zou, J.Liang, G.Zhang, F.Zhang, S.Davey, K.Guo, Z.2023-11-082023-11-082023Advanced Materials, 2023; 35(49):2210671-1-2210671-330935-96481521-4095https://hdl.handle.net/2440/139851Published online: October 22, 2023Rechargeable lithium-carbon dioxide (Li–CO₂) batteries are promising devices for CO₂ recycling and energy storage. However, thermodynamically stable and electrically insulating discharge products (DPs) (e.g., Li₂CO₃) deposited at cathodes require rigorous conditions for completed decomposition, resulting in large recharge polarization and poor battery reversibility. Although progress has been achieved in cathode design and electrolyte optimization, the significance of DPs is generally underestimated. Therefore, it is necessary to revisit the role of DPs in Li–CO₂ batteries to boost overall battery performance. Here, a critical and systematic review of DPs in Li–CO₂ batteries is reported for the first time. Fundamentals of reactions for formation and decomposition of DPs are appraised; impacts on battery performance including overpotential, capacity, and stability are demonstrated; and the necessity of discharge product management is highlighted. Practical in situ/operando technologies are assessed to characterize reaction intermediates and the corresponding DPs for mechanism investigation. Additionally, achievable control measures to boost the decomposition of DPs are evidenced to provide battery design principles and improve the battery performance. Findings from this work will deepen the understanding of electrochemistry of Li–CO₂ batteries and promote practical applications.en© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.CO2 recyclingdischarge productsenergy storageLi-CO2 batteriesproduct formation and decompositionJournal article10.1002/adma.2022106712023-11-08644275Liang, G. [0000-0002-2302-4932]Zhang, S. [0000-0002-3268-5708]Davey, K. [0000-0002-7623-9320]Guo, Z. [0000-0003-3464-5301]