A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes

Abstract

Silicon is an attractive material for anodes in energy storage devices1,2,3, because it has ten times the theoretical capacity of its state-of-the-art carbonaceous counterpart. Silicon anodes can be used both in traditional lithium-ion batteries and in more recent Li–O2 and Li–S batteries as a replacement for the dendrite-forming lithium metal anodes. The main challenges associated with silicon anodes are structural degradation and instability of the solid-electrolyte interphase caused by the large volume change (300%) during cycling, the occurrence of side reactions with the electrolyte, and the low volumetric capacity when the material size is reduced to a nanometre scale4,5,6,7. Here, we propose a hierarchical structured silicon anode that tackles all three of these problems. Our design is inspired by the structure of a pomegranate, where single silicon nanoparticles are encapsulated by a conductive carbon layer that leaves enough room for expansion and contraction following lithiation and delithiation. An ensemble of these hybrid nanoparticles is then encapsulated by a thicker carbon layer in micrometre-size pouches to act as an electrolyte barrier. As a result of this hierarchical arrangement, the solid-electrolyte interphase remains stable and spatially confined, resulting in superior cyclability (97% capacity retention after 1,000 cycles). In addition, the microstructures lower the electrode–electrolyte contact area, resulting in high Coulombic efficiency (99.87%) and volumetric capacity (1,270 mAh cm−3), and the cycling remains stable even when the areal capacity is increased to the level of commercial lithium-ion batteries (3.7 mAh cm−2).

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Figure 1: Schematic of the pomegranate-inspired design.
Figure 2: Fabrication and characterization of silicon pomegranates.
Figure 3: Tuning the size of the void space of silicon pomegranates and in situ TEM characterization during lithiation.
Figure 4: Electrochemical characterization of silicon pomegranate anodes.

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Acknowledgements

Y.C. acknowledges support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy (contract no. DE-AC02-05CH11231, subcontract no. 6951379) under the Batteries for Advanced Transportation Technologies (BATT) Program. M.T.M. acknowledges the National Science Foundation Graduate Fellowship Program and the Stanford Graduate Fellowship Program. H.W.L. acknowledges the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (contract no. 2012038593). The authors thank Z. Chen for discussions, F. Wei for providing the carbon nanotubes and Croda for providing the emulsifier.

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N.L., Z.L. and Y.C. conceived the concept and experiments. N.L. and Z.L. carried out the synthesis and performed materials characterization and electrochemical measurements. J.Z. participated in part of the synthesis and electrochemical measurements. M.T.M. and H.W.L. conducted in situ TEM characterization. W.Z. conducted focused ion beam experiments. N.L., Z.L. and Y.C. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Yi Cui.

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The authors declare no competing financial interests.

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Liu, N., Lu, Z., Zhao, J. et al. A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. Nature Nanotech 9, 187–192 (2014). https://doi.org/10.1038/nnano.2014.6

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