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Degradation-resistant TiO2@Sn anodes for high-capacity lithium-ion batteries

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Abstract

As the demand for higher-performance batteries has increased, so has the body of research on theoretical high-capacity anode materials. However, the research has been hindered because the high-capacity anode material properties and interactions are not well understood, largely due to the difficulty of observing cycling in situ. Using electrochemical scanning transmission electron microscopy (ec-STEM), we report the real-time observation and electrochemical analysis of pristine tin (Sn) and titanium dioxide-coated Sn (TiO2@Sn) electrodes during lithiation/delithiation. As expected, we observed a volume expansion of the pristine Sn electrodes during lithiation, but we further observed that the expansion was followed by Sn detachment from the current collector. Remarkably, although the TiO2@Sn electrodes also exhibited similar volume expansion during lithiation, they showed no evidence of Sn detachment. We found that the TiO2 surface layer acted as an electrochemically activated artificial solid-electrolyte interphase that serves to conduct Li ions. As a physical coating, it mechanically prevented Sn detachment following volume changes during cycling, providing significant degradation resistance and 80% Coulombic efficiency for a complete lithiation/delithiation cycle. Interestingly, upon delithiation, TiO2@Sn electrode displayed a self-healing mechanism of small pore formation in the Sn particle followed by agglomeration into several larger pores as delithiation continued.

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Author information

Authors and Affiliations

  1. Nanoscale Sciences, Sandia National Laboratories, Albuquerque, NM, 87185, USA

    Subrahmanyam Goriparti & Katharine L. Harrison

  2. Center for Integrated Nanotechnologies, Sandia National Laboratories, Albuquerque, NM, 87185, USA

    Katherine L. Jungjohann

Authors
  1. Subrahmanyam Goriparti
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  2. Katharine L. Harrison
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  3. Katherine L. Jungjohann
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Corresponding author

Correspondence to Katherine L. Jungjohann.

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Supplementary Information

Below is the link to the electronic supplementary material.

10853_2021_6265_MOESM1_ESM.docx

HAADF images, EDS mapping of TiO2@Sn electrode, Coulombic efficiency vs cycle number of pristine Sn and TiO2@Sn electrodes, additional replicate experiments, and estimate of volume changes after lithiation of TiO2@Sn electrode (DOCX 4432 kb)

Full pristine Sn electrode lithiation with grain size about 50–100 nm at current 1 mA/cm2 (AVI 4113 kb)

Full pristine Sn electrode lithiation with grain size about 500 nm-1 µm at current 1 mA/cm2 (AVI 150 kb)

Full TiO2@Sn electrode lithiation grain size about 500 nm-1 µm at current 1 mA/cm2 (AVI 42 kb)

Full TiO2@Sn electrode delithiation grain size about 500 nm-1 µm at current 1 mA/cm2 (AVI 29 kb)

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Goriparti, S., Harrison, K.L. & Jungjohann, K.L. Degradation-resistant TiO2@Sn anodes for high-capacity lithium-ion batteries. J Mater Sci 56, 17156–17166 (2021). https://doi.org/10.1007/s10853-021-06265-7

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  • DOI: https://doi.org/10.1007/s10853-021-06265-7

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