Nanostructuring has been shown to be fruitful in addressing the problems of high-capacity Si anodes. However, issues with the high cost and poor Coulombic efficiencies of nanostructured Si still need to be resolved. Si microparticles are a low-cost alternative but, unlike Si nanoparticles, suffer from unavoidable particle fracture during electrochemical cycling, thus making stable cycling in a real battery impractical. Here we introduce a method to encapsulate Si microparticles (∼1–3 µm) using conformally synthesized cages of multilayered graphene. The graphene cage acts as a mechanically strong and flexible buffer during deep galvanostatic cycling, allowing the microparticles to expand and fracture within the cage while retaining electrical connectivity on both the particle and electrode level. Furthermore, the chemically inert graphene cage forms a stable solid electrolyte interface, minimizing irreversible consumption of lithium ions and rapidly increasing the Coulombic efficiency in the early cycles. We show that even in a full-cell electrochemical test, for which the requirements of stable cycling are stringent, stable cycling (100 cycles; 90% capacity retention) is achieved with the graphene-caged Si microparticles.
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Y.L. acknowledges the National Science Foundation Graduate Fellowship Program for funding and M. Hanna for fruitful discussions. 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). Y.C. acknowledges the support from the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of Vehicle Technologies of the US Department of Energy under the Battery Materials Research (BMR) Program.
The authors declare no competing financial interests.
Supplementary Methods, Supplementary Figures 1-13, Supplementary. (PDF 1406 kb)
External load testing for empty amorphous carbon shell. The fragile coating breaks after only a slight deformation. (MP4 1577 kb)
External load testing for empty graphene cage. Despite extreme compression, the graphene cage is able to fully collapse its shape and still returns to its original structure after deloading. (MP4 2429 kb)
Lithiation of a graphene-encapsulated SiMP. Note that the particle expansion and fracture are quite violent and anisotropic. Despite this, the graphene cage remains undamaged and electrically connects the fractured particles within. Movie is x10 speed. (MOV 9095 kb)
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Li, Y., Yan, K., Lee, HW. et al. Growth of conformal graphene cages on micrometre-sized silicon particles as stable battery anodes. Nat Energy 1, 15029 (2016). https://doi.org/10.1038/nenergy.2015.29
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