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Title: Nanostructural and Electrochemical Evolution of the Solid-Electrolyte Interphase on CuO Nanowires Revealed by Cryogenic-Electron Microscopy and Impedance Spectroscopy

Abstract

Battery performance is critically dependent on the nanostructure and electrochemical properties of the solid-electrolyte interphase (SEI)—a passivation film that exists on most lithium-battery anodes. However, knowledge of how the SEI nanostructure forms and its impact on ionic transport remains limited due to its sensitivity to transmission electron microscopy and difficulty in accurately probing the SEI impedance. Here, we track the voltage-dependent, stepwise evolution of the nanostructure and impedance of the SEI on CuO nanowires using cryogenic-electron microscopy (cryo-EM) and electrochemical impedance spectroscopy (EIS). In carbonate electrolyte, the SEI forms at 1.0 V vs Li/Li+ as a 3 nm thick amorphous SEI and grows to 4 nm at 0.5 V; as the potential approaches 0.0 V vs Li/Li+, the SEI on the CuO nanowires forms an 8 nm thick inverted multilayered nanostructure in ethylene carbonate/diethyl carbonate (EC/DEC) electrolyte with 10 vol % fluoroethylene carbonate (FEC) and a mosaic nanostructure in EC/DEC electrolyte. Upon Li deposition, the total SEI thickness grows to 16 nm, and significant growth of the inner amorphous layer takes place in the inverted multilayered nanostructure, indicating that electrolyte permeates the SEI. Using a refined EIS methodology, we isolate the SEI impedance on Cu and find that the SEImore » nanostructure directly correlates to macroscopic Li-ion transport through the SEI. The inverted layered nanostructure decreases the interfacial impedance upon formation, whereas the mosaic nanostructure continually increases the interfacial impedance during growth. Furthermore these structural and electrochemical findings illustrate a more complete portrait of SEI formation and guide further improvements in engineered SEI.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Stanford Univ., Stanford, CA (United States)
  2. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1503645
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 13; Journal Issue: 1; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; batteries; cryogenic-electron microscopy; lithium-ion batteries; lithium-metal anode; solid-electrolyte interphase; transmission electron microscopy

Citation Formats

Huang, William, Boyle, David T., Li, Yuzhang, Li, Yanbin, Pei, Allen, Chen, Hao, and Cui, Yi. Nanostructural and Electrochemical Evolution of the Solid-Electrolyte Interphase on CuO Nanowires Revealed by Cryogenic-Electron Microscopy and Impedance Spectroscopy. United States: N. p., 2018. Web. doi:10.1021/acsnano.8b08012.
Huang, William, Boyle, David T., Li, Yuzhang, Li, Yanbin, Pei, Allen, Chen, Hao, & Cui, Yi. Nanostructural and Electrochemical Evolution of the Solid-Electrolyte Interphase on CuO Nanowires Revealed by Cryogenic-Electron Microscopy and Impedance Spectroscopy. United States. https://doi.org/10.1021/acsnano.8b08012
Huang, William, Boyle, David T., Li, Yuzhang, Li, Yanbin, Pei, Allen, Chen, Hao, and Cui, Yi. 2018. "Nanostructural and Electrochemical Evolution of the Solid-Electrolyte Interphase on CuO Nanowires Revealed by Cryogenic-Electron Microscopy and Impedance Spectroscopy". United States. https://doi.org/10.1021/acsnano.8b08012. https://www.osti.gov/servlets/purl/1503645.
@article{osti_1503645,
title = {Nanostructural and Electrochemical Evolution of the Solid-Electrolyte Interphase on CuO Nanowires Revealed by Cryogenic-Electron Microscopy and Impedance Spectroscopy},
author = {Huang, William and Boyle, David T. and Li, Yuzhang and Li, Yanbin and Pei, Allen and Chen, Hao and Cui, Yi},
abstractNote = {Battery performance is critically dependent on the nanostructure and electrochemical properties of the solid-electrolyte interphase (SEI)—a passivation film that exists on most lithium-battery anodes. However, knowledge of how the SEI nanostructure forms and its impact on ionic transport remains limited due to its sensitivity to transmission electron microscopy and difficulty in accurately probing the SEI impedance. Here, we track the voltage-dependent, stepwise evolution of the nanostructure and impedance of the SEI on CuO nanowires using cryogenic-electron microscopy (cryo-EM) and electrochemical impedance spectroscopy (EIS). In carbonate electrolyte, the SEI forms at 1.0 V vs Li/Li+ as a 3 nm thick amorphous SEI and grows to 4 nm at 0.5 V; as the potential approaches 0.0 V vs Li/Li+, the SEI on the CuO nanowires forms an 8 nm thick inverted multilayered nanostructure in ethylene carbonate/diethyl carbonate (EC/DEC) electrolyte with 10 vol % fluoroethylene carbonate (FEC) and a mosaic nanostructure in EC/DEC electrolyte. Upon Li deposition, the total SEI thickness grows to 16 nm, and significant growth of the inner amorphous layer takes place in the inverted multilayered nanostructure, indicating that electrolyte permeates the SEI. Using a refined EIS methodology, we isolate the SEI impedance on Cu and find that the SEI nanostructure directly correlates to macroscopic Li-ion transport through the SEI. The inverted layered nanostructure decreases the interfacial impedance upon formation, whereas the mosaic nanostructure continually increases the interfacial impedance during growth. Furthermore these structural and electrochemical findings illustrate a more complete portrait of SEI formation and guide further improvements in engineered SEI.},
doi = {10.1021/acsnano.8b08012},
url = {https://www.osti.gov/biblio/1503645}, journal = {ACS Nano},
issn = {1936-0851},
number = 1,
volume = 13,
place = {United States},
year = {2018},
month = {12}
}

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Works referencing / citing this record:

Key Aspects of Lithium Metal Anodes for Lithium Metal Batteries
journal, March 2019


Uniform High Ionic Conducting Lithium Sulfide Protection Layer for Stable Lithium Metal Anode
journal, April 2019