Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy

Leenheer, Andrew J.; Jungjohann, Katherine L.; Zavadil, Kevin R.; Harris, Charles T.

doi:10.1021/acsnano.6b02200

Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy

Journal Article · Tue May 31 00:00:00 EDT 2016 · ACS Nano

DOI:https://doi.org/10.1021/acsnano.6b02200· OSTI ID:1265168

Leenheer, Andrew J. ^[1]; Jungjohann, Katherine L. ^[1]; Zavadil, Kevin R. ^[1]; Harris, Charles T. ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Battery cycle life is directly influenced by the microstructural changes occurring in the electrodes during charge and discharge cycles. In this study, we image in situ the nanoscale phase evolution in negative electrode materials for Li-ion batteries using a fully enclosed liquid cell in a transmission electron microscope (TEM) to reveal early degradation that is not evident in the charge–discharge curves. To compare the electrochemical phase transformation behavior between three model materials, thin films of amorphous Si, crystalline Al, and crystalline Au were lithiated and delithiated at controlled rates while immersed in a commercial liquid electrolyte. This method allowed for the direct observation of lithiation mechanisms in nanoscale negative electrodes, revealing that a simplistic model of a surface-to-interior lithiation front is insufficient. For the crystalline films, a lithiation front spread laterally from a few initial nucleation points, with continued grain nucleation along the growing interface. The intermediate lithiated phases were identified using electron diffraction, and high-resolution postmortem imaging revealed the details of the final microstructure. Lastly, our results show that electrochemically induced solid–solid phase transformations can lead to highly concentrated stresses at the laterally propagating phase boundary which should be considered for future designs of nanostructured electrodes for Li-ion batteries.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES); Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC04-94AL85000; SC0001160

OSTI ID:: 1265168

Report Number(s):: SAND2016--6066J; 644958

Journal Information:: ACS Nano, Journal Name: ACS Nano Journal Issue: 6 Vol. 10; ISSN 1936-0851

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Phase Boundary Propagation in Li-Alloying Battery Electrodes Revealed by Liquid-Cell Transmission Electron Microscopy

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