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Title: Final Report: In-Situ TEM Observations of Degradation Mechanisms in Next-Generation High-Energy Density Lithium-Ion Battery Systems

Abstract

This project originally sought to characterize nanoscale processes associated with the degradation of next-generation high energy density lithium-ion battery electrodes via in-situ transmission electron microscopy (TEM). The research also focused on developing the experimental techniques necessary for investigating electrochemical systems by in-situ transmission electron microscopy and providing a framework for understanding and quantifying electron beam effects that influence experimental results. In line with these goals, this project demonstrated and published the first in-situ TEM cycling of a Li-ion battery electrode in commercially relevant non-aqueous electrolyte: a technique subsequently adopted by a number of researchers in the field. Experiments performed on Sn anodes, demonstrated porosity evolution during Li dealloying as a mechanism for strain accommodation during the first cycle, and observed partially reversible crystalline to amorphous phase transitions associated with Li insertion and extraction in subsequent cycles. Complementary study of in-situ dealloying in a simple model, Au-Cu, was also performed. We also published the earliest quantitative measurements of electron beam effects in aqueous and non-aqueous liquids. Specifically, we utilized a model system to quantify the fraction of incident electron beam that contributed to charge transfer mediated reactions in non-aqueous liquid, since such liquids are primarily dose sensitive. We also quantified themore » evolution of model aqueous chemistries as a function of dose rate and chemical potential to better understand the reaction mechanisms active in liquids exposed to electron beams. The original project goals included the use of controlled environments to simulate different battery operational conditions. To aid such experiments, we developed new experimental apparatuses and techniques to perform in-situ liquid cell TEM under controlled temperature, including heating and cooling. We demonstrated this capability in aqueous systems; specifically understanding phase selection and solid-liquid interface interactions with particles during water crystallization and hydrothermal precipitation kinetics of ZnO. We also published the first demonstration of in-situ TEM based high-field (plasma) experiments and in-situ TEM of aqueous photochemistry, which demonstrated an previously unrecognized early growth mode transition during Au sputtering and delocalization of gas bubble nucleation during water splitting, respectively. In addition to the scientific results, this portion of the project greatly expanded the range of systems that can be characterized in realistic environments at the nanoscale via in-situ TEM. Unfortunately, commercial battery electrolytes are quite sensitive to electron dose. This limits the time of acquisition and/or the spatial resolution of the experiments. The same problem has been encountered in all subsequent publications in the field. The major problem, relative to the project original goals, is that long term cycling is challenging to characterize and the desired high resolution or analytical capabilities are limited. In line with our original goals to characterize battery reaction and degradation mechanisms under controlled electrochemical cycling, we developed a completely new type of Li-ion electrochemical cell that has been useful for both structural and analytical characterization. To date, we have demonstrated this platform for in-situ cycling of Li-ion batteries during scanning electron microscopy (SEM), Auger electron spectroscopy (AES), and x-ray photoelectron spectroscopy (XPS). In-situ AES has been found to be a quite powerful tool to characterize the chemical evolution of Li-ion batteries cycled in-situ and much of our effort in the final project period has focused on charactering Li-ion cathodes using the technique. We utilized in-situ SEM to propose a new mechanism for Li whisker/dendrite formation and show the importance of diffusion mediated stress relaxation in fracture of Sn anode particles. A combination of in-situ XPS and AES was used to clarify the CuO anode reaction mechanism. In the final project period, we have gained new insights into surface reactions occurring on cathodes at high voltage using in-situ AES. Specifically, we have discovered that many of the SEI formation reactions typically attributed to electrolyte decomposition are actually more fundamental to the electrode material surface thermodynamics in the presence of an arbitrary carbon source. These insights greatly affect how we understand and control surface degradation induced capacity fade at cathodes. Finally, we have made some effort to apply this novel in-situ platform to TEM characterization and believe this is a fruitful avenue for future research.« less

Authors:
ORCiD logo [1]
  1. Univ. of Illinois, Urbana-Champaign, IL (United States)
Publication Date:
Research Org.:
Univ. of Illinois, Urbana-Champaign, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1406527
Report Number(s):
DOE-UIUC-DE-SC0006509
DOE Contract Number:  
SC0006509
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Dillon, Shen J. Final Report: In-Situ TEM Observations of Degradation Mechanisms in Next-Generation High-Energy Density Lithium-Ion Battery Systems. United States: N. p., 2017. Web. doi:10.2172/1406527.
Dillon, Shen J. Final Report: In-Situ TEM Observations of Degradation Mechanisms in Next-Generation High-Energy Density Lithium-Ion Battery Systems. United States. doi:10.2172/1406527.
Dillon, Shen J. Thu . "Final Report: In-Situ TEM Observations of Degradation Mechanisms in Next-Generation High-Energy Density Lithium-Ion Battery Systems". United States. doi:10.2172/1406527. https://www.osti.gov/servlets/purl/1406527.
@article{osti_1406527,
title = {Final Report: In-Situ TEM Observations of Degradation Mechanisms in Next-Generation High-Energy Density Lithium-Ion Battery Systems},
author = {Dillon, Shen J.},
abstractNote = {This project originally sought to characterize nanoscale processes associated with the degradation of next-generation high energy density lithium-ion battery electrodes via in-situ transmission electron microscopy (TEM). The research also focused on developing the experimental techniques necessary for investigating electrochemical systems by in-situ transmission electron microscopy and providing a framework for understanding and quantifying electron beam effects that influence experimental results. In line with these goals, this project demonstrated and published the first in-situ TEM cycling of a Li-ion battery electrode in commercially relevant non-aqueous electrolyte: a technique subsequently adopted by a number of researchers in the field. Experiments performed on Sn anodes, demonstrated porosity evolution during Li dealloying as a mechanism for strain accommodation during the first cycle, and observed partially reversible crystalline to amorphous phase transitions associated with Li insertion and extraction in subsequent cycles. Complementary study of in-situ dealloying in a simple model, Au-Cu, was also performed. We also published the earliest quantitative measurements of electron beam effects in aqueous and non-aqueous liquids. Specifically, we utilized a model system to quantify the fraction of incident electron beam that contributed to charge transfer mediated reactions in non-aqueous liquid, since such liquids are primarily dose sensitive. We also quantified the evolution of model aqueous chemistries as a function of dose rate and chemical potential to better understand the reaction mechanisms active in liquids exposed to electron beams. The original project goals included the use of controlled environments to simulate different battery operational conditions. To aid such experiments, we developed new experimental apparatuses and techniques to perform in-situ liquid cell TEM under controlled temperature, including heating and cooling. We demonstrated this capability in aqueous systems; specifically understanding phase selection and solid-liquid interface interactions with particles during water crystallization and hydrothermal precipitation kinetics of ZnO. We also published the first demonstration of in-situ TEM based high-field (plasma) experiments and in-situ TEM of aqueous photochemistry, which demonstrated an previously unrecognized early growth mode transition during Au sputtering and delocalization of gas bubble nucleation during water splitting, respectively. In addition to the scientific results, this portion of the project greatly expanded the range of systems that can be characterized in realistic environments at the nanoscale via in-situ TEM. Unfortunately, commercial battery electrolytes are quite sensitive to electron dose. This limits the time of acquisition and/or the spatial resolution of the experiments. The same problem has been encountered in all subsequent publications in the field. The major problem, relative to the project original goals, is that long term cycling is challenging to characterize and the desired high resolution or analytical capabilities are limited. In line with our original goals to characterize battery reaction and degradation mechanisms under controlled electrochemical cycling, we developed a completely new type of Li-ion electrochemical cell that has been useful for both structural and analytical characterization. To date, we have demonstrated this platform for in-situ cycling of Li-ion batteries during scanning electron microscopy (SEM), Auger electron spectroscopy (AES), and x-ray photoelectron spectroscopy (XPS). In-situ AES has been found to be a quite powerful tool to characterize the chemical evolution of Li-ion batteries cycled in-situ and much of our effort in the final project period has focused on charactering Li-ion cathodes using the technique. We utilized in-situ SEM to propose a new mechanism for Li whisker/dendrite formation and show the importance of diffusion mediated stress relaxation in fracture of Sn anode particles. A combination of in-situ XPS and AES was used to clarify the CuO anode reaction mechanism. In the final project period, we have gained new insights into surface reactions occurring on cathodes at high voltage using in-situ AES. Specifically, we have discovered that many of the SEI formation reactions typically attributed to electrolyte decomposition are actually more fundamental to the electrode material surface thermodynamics in the presence of an arbitrary carbon source. These insights greatly affect how we understand and control surface degradation induced capacity fade at cathodes. Finally, we have made some effort to apply this novel in-situ platform to TEM characterization and believe this is a fruitful avenue for future research.},
doi = {10.2172/1406527},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2017},
month = {11}
}

Works referenced in this record:

In Situ Scanning Electron Microscopy Characterization of the Mechanism for Li Dendrite Growth
journal, January 2016

  • Tang, Ching-Yen; Dillon, Shen J.
  • Journal of The Electrochemical Society, Vol. 163, Issue 8
  • DOI: 10.1149/2.0891608jes

In situ X-ray photoelectron and Auger electron spectroscopic characterization of reaction mechanisms during Li-ion cycling
journal, January 2016

  • Tang, Ching-Yen; Haasch, Richard T.; Dillon, Shen J.
  • Chemical Communications, Vol. 52, Issue 90
  • DOI: 10.1039/c6cc08176b

Mechano-Electrochemical Interaction Gives Rise to Strain Relaxation in Sn Electrodes
journal, January 2016

  • Barai, Pallab; Huang, Bo; Dillon, Shen J.
  • Journal of The Electrochemical Society, Vol. 163, Issue 14
  • DOI: 10.1149/2.0801614jes

Grain Boundary Parting Limit during Dealloying: Grain Boundary Parting Limit during Dealloying
journal, June 2014

  • Noh, Kyong Wook; Tai, Kaiping; Mao, Shimin
  • Advanced Engineering Materials, Vol. 17, Issue 2
  • DOI: 10.1002/adem.201400179

Comparative Study of Li and Na Electrochemical Reactions with Iron Oxide Nanowires
journal, February 2014


In Situ Cryogenic Transmission Electron Microscopy for Characterizing the Evolution of Solidifying Water Ice in Colloidal Systems
journal, February 2014


In-situ EM Characterization of Li-ion Battery through Multiple Cycles
journal, August 2014


Structural evolution of α-Fe2O3 nanowires during lithiation and delithiation
journal, January 2014


Growth Kinetics and Morphological Evolution of ZnO Precipitated from Solution
journal, July 2013

  • Liu, Yin; Tai, Kaiping; Dillon, Shen J.
  • Chemistry of Materials, Vol. 25, Issue 15
  • DOI: 10.1021/cm303522z

Integration of microplasma with transmission electron microscopy: Real-time observation of gold sputtering and island formation
journal, February 2013

  • Tai, K.; Houlahan, T. J.; Eden, J. G.
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep01325

Morphological changes in and around Sn electrodes during Li ion cycling characterized by in situ environmental TEM
journal, November 2013


Electron beam induced deposition of silicon nanostructures from a liquid phase precursor
journal, September 2012