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Reversible LiOH chemistry in Li-O2 batteries with free-standing Ag/δ-MnO2 nanoflower cathode

锂氧电池中基于自支撑Ag/δ-MnO2纳米花正极的可逆LiOH化学

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Abstract

The low energy efficiency and poor cycle stability arising from the high aggressivity of discharge products toward organic electrolytes limit the practical applications of Li-O2 batteries (LOBs). Compared with the typical discharge product Li2O2, LiOH shows better chemical and electrochemical stability. In this study, a free-standing cathode composed of hydrangea-like δ-MnO2 with Ag nanoparticles (NPs) embedded in carbon paper (CP) (Ag/δ-MnO2@CP) is fabricated and used as the catalyst for the reversible formation and decomposition of LiOH. The possible discharge mechanism is investigated by in situ Raman measurement and density functional theory calculation. Results confirm that δ-MnO2 dominantly catalyzes the conversion reaction of discharge intermediate LiO2* to LiOH and that Ag particles promote its catalytic ability. In the presence of Ag/δ-MnO2@CP cathode, the LOB exhibits enhanced specific capacity and a high discharge voltage plateau under humid O2 atmosphere. At a current density of 200 mA g−1, the LOB with the Ag/δ-MnO2@CP cathode presents an overpotential of 0.5 V and an ultra-long cycle life of 867 cycles with a limited specific capacity of 500 mA h g−1. This work provides a fresh view on the role of solid catalysts in LOBs and promotes the development of LOBs based on LiOH discharge product for practical applications.

摘要

因放电产物对有机电解液具有高攻击性, 使得锂-氧电池能量效率低和循环稳定性差的问题一直限制着其实际应用. 与典型放电产物过氧化锂相比, 氢氧化锂(LiOH)具有更好的化学和电化学稳定性. 本文通过在碳纸上原位生长嵌有纳米银的花状二氧化锰作为锂-氧电池的正极(Ag/δ-MnO2@CP), 并证明了它能催化LiOH的可逆生成和分解. 原位拉曼测试和理论计算表明Ag/δ-MnO2催化放电中间体LiO2*与水分子解离的H+反应最终生成LiOH. 以Ag/δ-MnO2@CP为正极的锂-氧电池在潮湿氧气环境下表现出更高的比容量和放电平台. 在电流密度为200 mA g−1 时, 锂-氧电池的过电位仅为0.5 V, 在500 mA h g−1的限制比容量下可循环867圈. 该工作为研究固相催化剂在锂-氧电池中的作用提供了新的思路, 并将促进基于LiOH放电产物的锂-氧电池的实际应用.

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Acknowledgements

This work was financially supported by the High-level Talents’ Discipline Construction Fund of Shandong University (31370089963078), the School Research Startup Expenses of Harbin Institute of Technology (Shenzhen) (20190037 and 20210028), China Postdoctoral Science Foundation (2019M661276 and 2021T140150), Guangdong Basic and Applied Basic Research Foundation (2019A1515110756), the National Natural Science Foundation of China (52002094), and the Open Fund of Guangdong Provincial Key laboratory of Advanced Energy Storage Materials (AESM202107).

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Authors and Affiliations

  1. Key Laboratory for Liquid-Solid Structural Evolution & Processing of Materials (Ministry of Education), Research Center for Carbon Nanomaterials, School of Materials Science and Engineering, Shandong University, Jinan, 250061, China

    Linna Dai  (代林娜), Qing Sun  (孙卿), Yuqing Yao  (姚雨晴), Huanhuan Guo  (郭焕焕), Xiangkun Nie  (聂祥坤), Jianwei Li  (李建伟), Pengchao Si  (司鹏超) & Lijie Ci  (慈立杰)

  2. State Key Laboratory of Advanced Welding and Joining, School of Materials Science and Engineering, Harbin Institute of Technology (Shenzhen), Shenzhen, 518055, China

    Deping Li  (李德平) & Lijie Ci  (慈立杰)

  3. School of Science, Harbin Institute of Technology (Shenzhen), Shenzhen, 518055, China

    Jingyu Lu  (陆敬予)

Authors
  1. Linna Dai  (代林娜)
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  2. Qing Sun  (孙卿)
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  3. Yuqing Yao  (姚雨晴)
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  4. Huanhuan Guo  (郭焕焕)
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  5. Xiangkun Nie  (聂祥坤)
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  6. Jianwei Li  (李建伟)
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  8. Jingyu Lu  (陆敬予)
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  9. Deping Li  (李德平)
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  10. Lijie Ci  (慈立杰)
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Contributions

Author contributions Dai L performed the experiments and wrote the manuscript; Sun Q performed some measurements and the data analysis; Yao Y contributed to material synthesis; Guo H, Nie X and Li J performed some formal analysis and analyzed the results; Lu J, Li D and Ci L revised the manuscript and directed the project.

Corresponding authors

Correspondence to Jingyu Lu  (陆敬予), Deping Li  (李德平) or Lijie Ci  (慈立杰).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Supporting data are available in the online version of the paper.

Linna Dai is currently a doctoral candidate at the School of Materials Science and Engineering, Shandong University. Her current research focuses on Li-air batteries.

Jingyu Lu is an assistant professor at Harbin Institute of Technology (HIT, Shenzhen), Shenzhen. He obtained his bachelor’s, master’s and PhD degrees from the Northwestern Polytechnical University, HIT, Nanyang Technological University, respectively. Then he did his postdoc research at the National University of Singapore, Harvard University, and University of Cambridge, before joining HIT (Shenzhen) in 2020. His research interests mainly include rechargeable batteries, in situ characterization techniques, and sensors.

Deping Li is currently an assistant professor at the School of Materials Science and Engineering, HIT (Shenzhen). He received his PhD degree in materials science and engineering from Shandong University under the supervision of Prof. Lijie Ci in 2019. His current research focuses on next-generation energy storage applications like solid-state batteries, potassium-ion batteries, and lithiumair batteries.

Lijie Ci is currently a full professor at the School of Materials Science and Engineering, HIT (Shenzhen). He received his PhD degree in mechanical engineering from Tsinghua University. He had been a researcher at the Institute of Physics, Chinese Academy of Sciences, Ecole Central Paris in France, Max Planck Institute for Metals in Germany, Rensselaer Polytechnic Institute, Rice University and Samsung Cheil Industry (San Jose Lab) in USA. Before he joined HIT (Shenzhen), he was a professor at Shandong University. His scientific interest focuses on carbon-based materials and energy storage devices.

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Dai, L., Sun, Q., Yao, Y. et al. Reversible LiOH chemistry in Li-O2 batteries with free-standing Ag/δ-MnO2 nanoflower cathode. Sci. China Mater. 65, 1431–1442 (2022). https://doi.org/10.1007/s40843-021-1929-5

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