Unraveling the Nanoscale Heterogeneity of Solid Electrolyte Interphase Using Tip-Enhanced Raman Spectroscopy

Nanda, Jagjit; Yang, Guang; Hou, Tingzheng; Voylov, Dmitry N.; Li, Xin; Ruther, Rose E.; Naguib, Michael; Persson, Kristin; Veith, Gabriel M.; Sokolov, Alexei P.

doi:10.1016/j.joule.2019.05.026

Title: Unraveling the Nanoscale Heterogeneity of Solid Electrolyte Interphase Using Tip-Enhanced Raman Spectroscopy

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Abstract

We employ tip-enhanced Raman spectroscopy (TERS) to study model amorphous silicon (a-Si) thin film anodes galvanostatically cycled for different numbers. For the 1× cycled a-Si, TERS shows good correlation between solid electrolyte interphase (SEI) topography and chemical mapping, corresponding to distribution of lithium ethylene dicarbonate (LEDC) and poly (ethylene oxide) (PEO)-like oligomer species. Subsequent electrochemical cycling makes the SEI relatively thick and rough with the chemical composition heavily dominated by LEDC monomer-dimer for 5× cycled a-Si. For 20× cycled a-Si, the TERS signal is dominated by carboxylate (RCO₂Li) compounds of various conformations and fluorinated species (Li_xPO_yF_z). A nanomosaic-multilayer hybrid SEI model on top of the a-Si anode is proposed. Here, the significance of this work is applicable not only to silicon, where SEI plays a dominant role in determining the cycle life performance and reversibility, but also for a number of other relevant battery chemistries such as Na-ion and multivalent redox systems.

Authors:

; Yang, Guang; Hou, Tingzheng; Voylov, Dmitry N.; Li, Xin; Ruther, Rose E.; Naguib, Michael; Persson, Kristin; Veith, Gabriel M.; Sokolov, Alexei P.

Publication Date:: Thu Aug 01 00:00:00 EDT 2019

Research Org.:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

OSTI Identifier:: 1648567

Alternate Identifier(s):: OSTI ID: 1557528; OSTI ID: 1564449

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Published Article

Journal Name:: Joule

Additional Journal Information:: Journal Name: Joule Journal Volume: 3 Journal Issue: 8; Journal ID: ISSN 2542-4351

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 42 ENGINEERING; solid electrolyte interphase; SEI; nanomosaic-multilayer model; tip-enhanced Raman spectroscopy; non-gap mode TERS; nanoscale heterogeneity; amorphous silicon anode; batteries; FDTD simulation; TERS mapping

Citation Formats


                    Nanda, Jagjit, Yang, Guang, Hou, Tingzheng, Voylov, Dmitry N., Li, Xin, Ruther, Rose E., Naguib, Michael, Persson, Kristin, Veith, Gabriel M., and Sokolov, Alexei P. Unraveling the Nanoscale Heterogeneity of Solid Electrolyte Interphase Using Tip-Enhanced Raman Spectroscopy.  United States: N. p., 2019. 
Web.  doi:10.1016/j.joule.2019.05.026.

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                    Nanda, Jagjit, Yang, Guang, Hou, Tingzheng, Voylov, Dmitry N., Li, Xin, Ruther, Rose E., Naguib, Michael, Persson, Kristin, Veith, Gabriel M., & Sokolov, Alexei P. Unraveling the Nanoscale Heterogeneity of Solid Electrolyte Interphase Using Tip-Enhanced Raman Spectroscopy.  United States.  https://doi.org/10.1016/j.joule.2019.05.026

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                    Nanda, Jagjit, Yang, Guang, Hou, Tingzheng, Voylov, Dmitry N., Li, Xin, Ruther, Rose E., Naguib, Michael, Persson, Kristin, Veith, Gabriel M., and Sokolov, Alexei P. Thu .  
"Unraveling the Nanoscale Heterogeneity of Solid Electrolyte Interphase Using Tip-Enhanced Raman Spectroscopy".  United States.  https://doi.org/10.1016/j.joule.2019.05.026.

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@article{osti_1648567,

  title        = {Unraveling the Nanoscale Heterogeneity of Solid Electrolyte Interphase Using Tip-Enhanced Raman Spectroscopy},

  author       = {Nanda, Jagjit and Yang, Guang and Hou, Tingzheng and Voylov, Dmitry N. and Li, Xin and Ruther, Rose E. and Naguib, Michael and Persson, Kristin and Veith, Gabriel M. and Sokolov, Alexei P.},

  abstractNote = {We employ tip-enhanced Raman spectroscopy (TERS) to study model amorphous silicon (a-Si) thin film anodes galvanostatically cycled for different numbers. For the 1× cycled a-Si, TERS shows good correlation between solid electrolyte interphase (SEI) topography and chemical mapping, corresponding to distribution of lithium ethylene dicarbonate (LEDC) and poly (ethylene oxide) (PEO)-like oligomer species. Subsequent electrochemical cycling makes the SEI relatively thick and rough with the chemical composition heavily dominated by LEDC monomer-dimer for 5× cycled a-Si. For 20× cycled a-Si, the TERS signal is dominated by carboxylate (RCO2Li) compounds of various conformations and fluorinated species (LixPOyFz). A nanomosaic-multilayer hybrid SEI model on top of the a-Si anode is proposed. Here, the significance of this work is applicable not only to silicon, where SEI plays a dominant role in determining the cycle life performance and reversibility, but also for a number of other relevant battery chemistries such as Na-ion and multivalent redox systems.},

  doi          = {10.1016/j.joule.2019.05.026},

  journal      = {Joule},

  number       = 8,

  volume       = 3,

  place        = {United States},

  year         = {Thu Aug 01 00:00:00 EDT 2019},

  month        = {Thu Aug 01 00:00:00 EDT 2019}

}

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