Applications and Challenges of Redox-Mediated Catalysis in Lithium-Air Batteries★

doi:10.6023/A25050180

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (11): 1414-1423.DOI: 10.6023/A25050180 Previous Articles Next Articles

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媒介体催化在锂-空气电池中的应用与挑战^★

何璐, 王硕, 陈宇辉^*()

南京工业大学化工学院材料化学工程全国重点实验室南京 211816

投稿日期:2025-05-19 发布日期:2025-07-21
通讯作者: 陈宇辉

作者简介:

陈宇辉, 2009年本科毕业于复旦大学化学系, 2014年博士毕业于英国圣安德鲁斯大学, 随后在牛津大学从事博士后工作, 2017年入职南京工业大学任教授, 研究集中于原位电化学光谱/质谱表征和锂氧电池反应机制. 在原位电化学差分质谱和锂氧电池中媒介体催化电极反应等方面积累了丰富经验, 并取得多项研究成果, 在Nat. Catal.、Nat. Energy、Nat. Mater.、Nat. Chem.及Nat. Commum.等期刊发表论文50余篇. 现兼任Energy Mater.编委、SusMat和Chin. Chem. Lett.青年编委.

^★“中国青年化学家”专辑.

基金资助:
项目受国家自然科学基金(52173173); 江苏省自然科学基金(BK20220051)

Applications and Challenges of Redox-Mediated Catalysis in Lithium-Air Batteries^★

He Lu, Wang Shuo, Chen Yuhui^*()

State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816

Received:2025-05-19 Published:2025-07-21
Contact: Chen Yuhui
About author:
^★For the VSI “Rising Stars in Chemistry”.
Supported by:
National Natural Science Foundation of China(52173173); Natural Science Foundation of Jiangsu Province(BK20220051)

Lithium-air batteries are considered promising candidates for the development of advanced energy storage systems due to their exceptionally high theoretical energy densities. Taking lithium-oxygen batteries as an example, their theoretical specific energy can reach up to 3500 Wh/kg. However, lithium-air batteries, including lithium-oxygen and lithium-carbon dioxide batteries, still face significant challenges on the cathode side, such as sluggish reaction kinetics, high overpotentials, and side reactions caused by electrolyte decomposition. During discharge, gaseous reactants such as O₂ or CO₂ are reduced at the cathode to form solid discharge products like peroxides, carbonates, or oxalates. These products typically possess poor electronic and ionic conductivity, which can passivate the electrode surface, leading to catalyst deactivation and capacity limitations. In the subsequent charging process, the poor “solid-solid” contact between the catalyst and these insulating discharge products makes them difficult to decompose efficiently, resulting in high overpotentials, low coulombic efficiency, and severe parasitic reactions. To address these issues, researchers have introduced redox mediator (RM) molecular catalysts to convert the “solid-solid” interface into a more efficient “solid-liquid-solid” interface. RMs transfer electrons between the electrode and the discharge products in solution phase, enabling their oxidation and fully decomposition, thereby improving the poor contact of “solid-solid” interface and significantly improving the electrochemical performance of lithium-air batteries. This review briefly introduces the current status and key challenges in lithium-air battery research and, using lithium-oxygen batteries as a representative system, systematically discusses the catalytic roles, mechanisms, and advantages and disadvantages of redox mediators during both discharge and charge processes. Furthermore, the design principles and technical barriers in developing ideal redox mediator catalysts are analyzed, and future perspectives for this research field are proposed.

Key words: lithium-air battery, redox mediator, molecular catalyst, solid-liquid-solid interface, electrode reaction kinetics

Cite this article

He Lu, Wang Shuo, Chen Yuhui. Applications and Challenges of Redox-Mediated Catalysis in Lithium-Air Batteries^★[J]. Acta Chimica Sinica, 2025, 83(11): 1414-1423.

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Fig. & Tab. 5

Figure 1. (a) Schematic illustration of O2 reduction in a Li-O2 cell [the solution pathway (blue) and the surface pathway (gray)[54]], and schematics of discharge process catalyzed by (b) DBBQ[34], (c) AQ[55] and (d) RB[57]

Figure 2. (a) Schematic illustration of Li2O2 decomposition catalyzed by the RM (the electron transfer steps highlighted by blue dashed boxes), (b) schematics of SECM feedback approach curves[62], (c) dependence of the apparent rate constant, kapp, on the redox potential, E0, of the mediators[62], (d) the kapp of $\mathrm{I}_{3}^{-}$ oxidizing Li2O2 with various E ($\mathrm{I}_{3}^{-}$/I－) in DMSO electrolyte containing LiTFSI[63]

Figure 3. (a) The role and (b) the possible catalyzed reaction routes of FePc as an RM in Li-O2 batteries[66], and (c) galvanostatic cycling performance of different transition-metal phthalocyanines as RMs in Li-O₂ batteries[68]

Figure 4. (a) Schematics and electrochemical performance of charging process catalyzed by TEMPO in Li-O2 batteries[73], and (b) UV-vis spectra observed at different states (marked by letters from B to F) during cycling of the porous carbon electrode in the TTF-containing Li-DMSO electrolyte[78]

Figure 5. Working processes of TEMPO and PTMA[80]

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媒介体催化在锂-空气电池中的应用与挑战^★

Applications and Challenges of Redox-Mediated Catalysis in Lithium-Air Batteries^★

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媒介体催化在锂-空气电池中的应用与挑战★

Applications and Challenges of Redox-Mediated Catalysis in Lithium-Air Batteries★

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媒介体催化在锂-空气电池中的应用与挑战^★

Applications and Challenges of Redox-Mediated Catalysis in Lithium-Air Batteries^★