Lithium metal is an attractive anode material for rechargeable batteries, owing to its high theoretical specific capacity of 3,860 mAh g−1. Despite extensive research efforts, there are still many fundamental challenges in using lithium metal in lithium-ion batteries. Most notably, critical information such as its nucleation and growth behaviour remains elusive. Here we explore the nucleation pattern of lithium on various metal substrates and unravel a substrate-dependent growth phenomenon that enables selective deposition of lithium metal. With the aid of binary phase diagrams, we find that no nucleation barriers are present for metals exhibiting a definite solubility in lithium, whereas appreciable nucleation barriers exist for metals with negligible solubility. We thereafter design a nanocapsule structure for lithium metal anodes consisting of hollow carbon spheres with nanoparticle seeds inside. During deposition, the lithium metal is found to predominantly grow inside the hollow carbon spheres. Such selective deposition and stable encapsulation of lithium metal eliminate dendrite formation and enable improved cycling, even in corrosive alkyl carbonate electrolytes, with 98% coulombic efficiency for more than 300 cycles.
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This work was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Battery Materials Research (BMR) Program in the Office of Vehicle Technologies of the US Department of Energy. H.-W.L. was supported by Basic Science Research Program through the National Research Foundation of Korea under Contract No. NRF-2012R1A6A3A03038593.
The authors declare no competing financial interests.
Supplementary Figures 1–7, Supplementary Reference. (PDF 4730 kb)
In-situ lithium melting. Two examples of in situ melting of lithium metal particles encapsuled inside a nanocapsule, after electrochemical deposition. Nanocapsules with a single gold nanoparticle enclosed were used for clarity. (MOV 11831 kb)
In-situ lithium filling into nanocapsules. Lithium deposition inside nanocapsules is revealed by in situ transmission electron microscopy. The set-up was biased at a constant potential. Because the resistance of the cell decreased as lithium was gradually injected into the carbon structure, the lithiation/lithium-plating speed accelerated during the test. The playback speed changed at the point when lithium started to plate, to compensate the actual speed change. (MOV 12509 kb)
In-situ lithium cycling in nanocapsules. In situ observation of lithium cycling inside a nanocapsule. Carbon shells with single gold nanoparticles were used here for clarity, although tiny gold nanoparticles still exist on the inner wall of the carbon shell, which altered the nucleation of lithium at the first cycle. The gold nanoparticle was able to dissolve in lithium metal completely due to e-beam heating. Precipitation of gold was confined within the identical carbon shell, although the exact position may be random. (MOV 21885 kb)
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Yan, K., Lu, Z., Lee, HW. et al. Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth. Nat Energy 1, 16010 (2016). https://doi.org/10.1038/nenergy.2016.10
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