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Rational design of redox mediators for advanced Li–O2 batteries

Nature Energy volume 1, Article number: 16066 (2016) Cite this article

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Abstract

The discovery of effective catalysts is an important step towards achieving Li–O2 batteries with long cycle life and high round-trip efficiency. Soluble-type catalysts or redox mediators (RMs) possess great advantages over conventional solid catalysts, generally exhibiting much higher efficiency. Here, we select a series of organic RM candidates as a model system to identify the key descriptor in determining the catalytic activities and stabilities in Li–O2 cells. It is revealed that the level of ionization energies, readily available parameters from a database of the molecules, can serve such a role when comparing with the formation energy of Li2O2 and the highest occupied molecular orbital energy of the electrolyte. It is demonstrated that they are critical in reducing the overpotential and improving the stability of Li–O2 cells, respectively. Accordingly, we propose a general principle for designing feasible catalysts and report a RM, dimethylphenazine, with a remarkably low overpotential and high stability.

The rapid growth of portable energy demands has increased interest in next-generation batteries with high energy densities. Among several post-lithium ion battery candidates, Li–O2 batteries have attracted tremendous attention because of their exceptionally high theoretical energy density ( ∼3,500 Wh kg−1)1,2,3,4. The absence of a transition metal and the use of abundant resources of oxygen in the electrochemical reaction further make this chemistry appealing as a promising future battery system5,6,7. However, the present state of Li–O2 batteries involves the critical limitations of low cycle life and high charging overpotential (low energy efficiency) during cycling8,9,10. Although the cycle life and high overpotential are believed to be correlated to each other to some extent, the origin of the latter is often attributed to several factors in the decomposition process of Li2O2, such as the sluggish oxygen evolution from the Li2O2 crystal, low electrical conductivity, and formation/decomposition of unwanted products, including Li2CO3 (refs 11,12,13,14). Furthermore, the solid discharge product (Li2O2) in Li–O2 batteries is irregularly formed on the electrode; thus, the porous air cathode is easily clogged, hindering the efficient transport of oxygen and ions, causing further overpotential15,16. Addressing these issues and enhancing the energy efficiency by decreasing the overpotential are indispensable in taking advantage of the high energy density of the Li–O2 battery chemistry.

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Figure 1: Role of RM for Li–O2 batteries.
Figure 2: Electrochemical properties of various RMs.
Figure 3: Gas analyses on effect of RMs.
Figure 4: Molecular orbital energies of RMs and TEGDME.
Figure 5: Cyclic voltammetry of RMs.
Figure 6: Effects of DMPZ as a catalyst for Li–O2 batteries.

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Acknowledgements

This work was supported by the HMC (Hyundai Motor Company), the Project Code (IBS-R006-G1), and the National Research Foundation of Korea(NRF) grant funded by the Korean Government(MSIP) (No. 2015R1A2A1A10055991). Y.Z. and K.C. acknowledge the Global Frontier R&D Program on Center for Multiscale Energy System (NRF-2011-0031571).

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Author notes

  1. Hee-Dae Lim and Byungju Lee: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Materials Science and Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic of Korea

    Hee-Dae Lim, Byungju Lee, Jihyun Hong, Jinsoo Kim, Youngmin Ko & Kisuk Kang

  2. Department of Mechanical & Aerospace Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic of Korea

    Yongping Zheng & Kyeongjae Cho

  3. Department of Materials Science and Engineering, University of Texas, Dallas, Richardson, Texas 75080, USA

    Yongping Zheng & Kyeongjae Cho

  4. Energy Lab, Material Research Center, Samsung Advanced Institute of Technology, Samsung Electronics Co. Ltd., 130 Samsung-ro, Yeongtong-gu, Suwon-si, Gyeonggi-do 16678, Republic of Korea

    Hyeokjo Gwon

  5. Chemical Engineering Department, Stanford University, Shriram Center, 443 Via Ortega, Stanford, California 94305-4125, USA

    Minah Lee

  6. Center for Nanoparticle Research, Institute for Basic Science (IBS), Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 151-742, Republic of Korea

    Kisuk Kang

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Contributions

H.-D.L. and Y.Z. designed the experiments with help from J.H., J.K., H.G., Y.K., M.L. and K.C. The computations were performed by B.L. The original idea was conceived by K.K., who supervised all the experiments and calculations. All the authors discussed the results and contributed to preparing the manuscript.

Corresponding authors

Correspondence to Kyeongjae Cho or Kisuk Kang.

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The authors declare no competing financial interests.

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Supplementary Figures 1–18, Supplementary Tables 1–2, Supplementary Notes 1–9, Supplementary References. (PDF 2205 kb)

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Lim, HD., Lee, B., Zheng, Y. et al. Rational design of redox mediators for advanced Li–O2 batteries. Nat Energy 1, 16066 (2016). https://doi.org/10.1038/nenergy.2016.66

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