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Non-encapsulation approach for high-performance Li–S batteries through controlled nucleation and growth

Nature Energy volume 2, pages 813–820 (2017)Cite this article

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Abstract

High-surface-area, nanostructured carbon is widely used for encapsulating sulfur and improving the cyclic stability of Li–S batteries, but the high carbon content and low packing density limit the specific energy that can be achieved. Here we report an approach that does not rely on sulfur encapsulation. We used a low-surface-area, open carbon fibre architecture to control the nucleation and growth of the sulfur species by manipulating the carbon surface chemistry and the solvent properties, such as donor number and Li+ diffusivity. Our approach facilitates the formation of large open spheres and prevents the production of an undesired insulating sulfur-containing film on the carbon surface. This mechanism leads to ~100% sulfur utilization, almost no capacity fading, over 99% coulombic efficiency and high energy density (1,835 Wh kg−1 and 2,317 Wh l−1). This finding offers an alternative approach for designing high-energy and low-cost Li–S batteries through controlling sulfur reaction on low-surface-area carbon.

The growing demand for high-energy-density energy storage for transportation and the grid has stimulated extensive research beyond Li-ion battery technologies1. Among these, Li–S batteries have attracted wide attention because of their high theoretical energy2,3. Despite intensive research, there are still significant obstacles to developing practical Li–S batteries4,5,6. The major challenges arise from the highly insulating S/Li2S and the dissolution of intermediate polysulfides during charge/discharge7,8. The former results in low sulfur utilization9,10 and the latter causes low coulombic efficiency and rapid capacity fading in Li–S batteries7.

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Fig. 1: Two different growth pathways of sulfur species during electrochemical process in Li–S batteries.
Fig. 2: Electrochemical profiles and the discharge product morphology of Li–S batteries with different electrode processes.
Fig. 3: Electrochemical performances of sulfur electrodes.
Fig. 4: Operando EIS analysis of Non-Encap-S/CF|Li and MD-Encap-S/CF|Li cells during cycling.
Fig. 5: Characterization of O2-plasma-treated CF electrodes.
Fig. 6: SEM images showing the Li2S morphologies on discharge with 1 M Li2S8 in different solvents.
Fig. 7: MD simulation and experimental diffusion measurements in different solvent systems.

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Acknowledgements

This work was supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES). The SEM images, XPS and NMR measurements were performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the US Department of Energy’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the Department of Energy under Contract DE-AC05-76RLO1830.

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Authors and Affiliations

  1. Joint Center for Energy Storage Research (JCESR), Pacific Northwest National Laboratory, Richland, WA, 99352, USA

    Huilin Pan, Junzheng Chen, Ruiguo Cao, Vijay Murugesan, Kee Sung Han, Ji-Guang Zhang, Karl T. Mueller, Yuyan Shao & Jun Liu

  2. Energy and Environmental Directorate, Pacific Northwest National Laboratory, Richland, WA, 99352, USA

    Huilin Pan, Junzheng Chen, Ruiguo Cao, Vijay Murugesan, Luis Estevez, Ji-Guang Zhang, Yuyan Shao & Jun Liu

  3. Lawrence Berkeley National Laboratory, Berkeley, CA, 94720, USA

    Nav Nidhi Rajput & Kristin Persson

  4. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, 99352, USA

    Kee Sung Han & Mark H. Engelhard

  5. Department of Materials Science and Engineering, University of California-Berkeley, Berkeley, CA, 94720, USA

    Kristin Persson

  6. Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, WA, 99352, USA

    Karl T. Mueller

  7. Department of Materials Science and Engineering, Stanford University, Stanford, CA, 94305, USA

    Yi Cui

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  1. Huilin Pan
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Contributions

H.P., Y.S. and J.L. conceived the research. H.P., Y.S., J.L. and Y.C. designed the experiments. H.P., J.C., R.C. and L.E. performed the experiments and measurements. V.M., K.H. and K.T.M. performed NMR. N.N.R. and K.P. performed MD simulation. M.H.E. performed XPS analysis. All authors discussed the results. K.P., J.-G.Z., K.T. and Y.C. revised the manuscript. H.P., Y.S. and J.L. wrote the paper with input from all authors.

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Correspondence to Yuyan Shao or Jun Liu.

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Pan, H., Chen, J., Cao, R. et al. Non-encapsulation approach for high-performance Li–S batteries through controlled nucleation and growth. Nat Energy 2, 813–820 (2017). https://doi.org/10.1038/s41560-017-0005-z

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