High-capacity alloy anode materials for Li-ion batteries have long been held back by limited cyclability caused by the large volume changes during lithium insertion and removal. Hollow and yolk-shell nanostructures have been used to increase the cycling stability by providing an inner void space to accommodate volume changes and a mechanically and dimensionally stable outer surface. These materials, however, require complex synthesis procedures. Here, using in situ transmission electron microscopy, we show that sufficiently small antimony nanocrystals spontaneously form uniform voids on the removal of lithium, which are then reversibly filled and vacated during cycling. This behaviour is found to arise from a resilient native oxide layer that allows for an initial expansion during lithiation but mechanically prevents shrinkage as antimony forms voids during delithiation. We developed a chemomechanical model that explains these observations, and we demonstrate that this behaviour is size dependent. Thus, antimony naturally evolves to form optimal nanostructures for alloy anodes, as we show through electrochemical experiments in a half-cell configuration in which 15-nm antimony nanocrystals have a consistently higher Coulombic efficiency than larger nanoparticles.
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The data that support the plots within this article and other findings of this study are available from the corresponding author upon reasonable request.
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This work was performed at the Georgia Tech Materials Characterization Facility and the Institute for Electronics and Nanotechnology, a member of the National Nanotechnology Coordinated Infrastructure, which is supported by the National Science Foundation (Grant ECCS-1542174). M.G.B. acknowledges support from the DOE Office of Science Graduate Student Research Program for research performed at Oak Ridge National Laboratory. A portion of this research was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility (K.A.U. and R.R.U.). M.T.M. acknowledges support from a Sloan Research Fellowship in Chemistry from the Alfred P. Sloan Foundation. M.Y. acknowledges financial support from the Swiss National Science foundation via an Ambizione Fellowship (no. 161249). M.G.B. acknowledges F. J. Q. Cortes for assistance with the Cr deposition and N. Kondekar for assistance with the diffraction analysis.
The authors declare no competing interests.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
(a) Group of pristine Sb crystals before cycling. (b) The same cluster after the first lithiation (i) and delithiation (ii). (c) After the second lithiation/delithiation. (d) After the third lithiation/delithiation. (e) After the fourth lithiation/delithiation. (f) After the fifth lithiation/delithiation. (g) After the sixth lithiation/delithiation. Since this is a larger group of particles compared to Supplementary Fig. 3, some particles are not fully lithiated or delithiated in each cycle due to transport limitations in the in situ experiment, resulting in a lack of volume change or hollowing behavior during that particular cycle.
Extended Data Fig. 2 Galvanostatic curves from Sb-based electrodes with different particle sizes at two different rates: 1 C (660 mA g−1) and C/10 (66 mA g−1).
(a, b) Data from 15-nm monodisperse nanocrystals at C/10 (a) and 1 C (b). (c, d) Data from 40-140 nm polydisperse nanoparticles at C/10 (c) and 1 C (d). (e, f) Data from bulk particles at C/10 (e) and 1 C (f). The curves at a rate of 1 C correspond to the specific capacity plots in Fig. 4b in the main text. All three samples at both rates show a discharge plateau at ~0.8 V vs. Li/Li+ and a charge plateau at ~1.0 V vs. Li/Li+, which are ascribed to the two-phase lithiation/delithiation of Sb. The small nanocrystals and larger nanoparticles show a higher plateau (~0.8–1.4 V vs. Li/Li+) during the initial discharge that corresponds to the conversion of the surface oxides to a lithiated phase (a, c). The nanocrystals exhibit a greater specific capacity associated with this oxide layer reaction (a) than the larger nanoparticles (c) due to the greater surface area of the nanocrystals.
Extended Data Fig. 3 Comparing in situ TEM sodiation/desodiation of Sb nanocrystals to lithiation/delithiation.
(a) TEM image of a group of Sb nanocrystals that have undergone sodiation. (b) Image of a different group of Sb nanocrystals that have been desodiated. (c) TEM image of a group of Sb nanocrystals that have undergone lithiation, and (d) the same group after delithiation. The morphology of the delithiated and desodiated particles is similar. In these images, it is clear that there is some merging of the oxide shells between particles after the reaction process, which is especially clear for the desodiation case (b). The metal regions within the oxide shells remain distinct, however.
Supplementary Figs. 1–15, Videos 1 and 2, Methods and refs. 1–3.
Supplementary Video 1 shows the volume expansion during the initial lithiation process of a group of Sb nanocrystals. This video is shown at 4 times the actual speed.
Supplementary Video 2 shows several lithiation and delithiation steps that the Sb nanocrystals in Fig. 2 underwent, starting with the second lithiation of the particles (the first cycle was not captured on video). This is followed by the delithiation process that is discussed and shown in detail in Fig. 2. Finally, the third lithiation step is shown as the voids are filled once more. This video is shown at 6 times the actual speed.
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Boebinger, M.G., Yarema, O., Yarema, M. et al. Spontaneous and reversible hollowing of alloy anode nanocrystals for stable battery cycling. Nat. Nanotechnol. 15, 475–481 (2020). https://doi.org/10.1038/s41565-020-0690-9
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