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Lithium Self-Discharge and Its Prevention: Direct Visualization through In Situ Electrochemical Scanning Transmission Electron Microscopy

Journal Article · · ACS Nano
 [1];  [1];  [1];  [2];  [2];  [3];  [4];  [5]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Joint Center for Energy Storage Research and Nanoscale Sciences
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Joint Center for Energy Storage Research; Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). MESA Fabrication Operations
  4. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Joint Center for Energy Storage Research; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Energy & Environmental Directorate
  5. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Joint Center for Energy Storage Research and Center for Integrated Nanotechnologies
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To understand the mechanism that controls low-aspect-ratio lithium deposition morphologies for Li-metal anodes in batteries, we conducted direct visualization of Li-metal deposition and stripping behavior through nanoscale in situ electrochemical scanning transmission electron microscopy (EC-STEM) and macroscale-cell electrochemistry experiments in a recently developed and promising solvate electrolyte, 4 M lithium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane. In contrast to published coin cell studies in the same electrolyte, our experiments revealed low Coulombic efficiencies and inhomogeneous Li morphology during in situ observation. In addition, we conclude that this discrepancy in Coulombic efficiency and morphology of the Li deposits was dependent on the presence of a compressed lithium separator interface, as we have confirmed through macroscale (not in the transmission electron microscope) electrochemical experiments. Our data suggests that cell compression changed how the solid-electrolyte interphase formed, which is likely responsible for improved morphology and Coulombic efficiency with compression. Furthermore, during the in situ EC-STEM experiments, we observed direct evidence of nanoscale self-discharge in the solvate electrolyte (in the state of electrical isolation). This self-discharge was duplicated in the macroscale, but it was less severe with electrode compression, likely due to a more passivating and corrosion-resistant solid-electrolyte interphase formed in the presence of compression. By combining the solvate electrolyte with a protective LiAl0.3S coating, we show that the Li nucleation density increased during deposition, leading to improved morphological uniformity. In conclusion, self-discharge was suppressed during rest periods in the cycling profile with coatings present, as evidenced through EC-STEM and confirmed with coin cell data.

Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
AC04-94AL85000; SC0001160; NA0003525
OSTI ID:
1411618
Alternate ID(s):
OSTI ID: 1512704
OSTI ID: 1426804
OSTI ID: 1430700
OSTI ID: 1648782
OSTI ID: 1481420
Report Number(s):
SAND--2017-12954J; 659164
Journal Information:
ACS Nano, Journal Name: ACS Nano Journal Issue: 11 Vol. 11; ISSN 1936-0851
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (10)

Recent Progress of In Situ Transmission Electron Microscopy for Energy Materials journal September 2019
Atomic and Molecular Layer Deposition for Superior Lithium-Sulfur Batteries: Strategies, Performance, and Mechanisms journal May 2018
Atomic and Molecular Layer Deposition for Superior Lithium-Sulfur Batteries: Strategies, Performance, and Mechanisms journal June 2018
Mechanistic understanding and strategies to design interfaces of solid electrolytes: insights gained from transmission electron microscopy journal May 2019
Fast galvanic lithium corrosion involving a Kirkendall-type mechanism journal January 2019
Origin of lithium whisker formation and growth under stress journal October 2019
Energy landscape of the charge transfer reaction at the complex Li/SEI/electrolyte interface journal January 2019
Rethinking How External Pressure Can Suppress Dendrites in Lithium Metal Batteries journal January 2019
Cryogenic specimens for nanoscale characterization of solid–liquid interfaces journal December 2019
Recent Progress of Metal–Air Batteries—A Mini Review journal July 2019

Figures / Tables (9)

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Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
artificial solid-electrolyte interphase
electrochemical transmission electron microscopy
lithium-ion batteries
lithium-metal anode
mechanical compression
protective coating
solid-electrolyte interphase