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Title: Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films

Abstract

A recently developed technique, electrochemical strain microscopy (ESM), utilizes the strong coupling between ionic current and anisotropic volumetric chemical expansion of lithium-ion electrode materials to dynamically probe the sub-one-hundred? nm inter-facial kinetic intercalation properties. A numerical technique based on the finite element method was developed to analyze the underlying physics that govern the ESM signal generation and establish relations to battery performance. The performed analysis demonstrates that the diffusion path within a thin film is tortuous and the extent of lithium diffusion into the electrode is dependent on the SPM-tip-imposed overpotential frequency. The detected surface actuation gives rise to the development of an electromechanical hysteresis loop whose shape is dependent on grain size and overpotential frequency. Shape and tilting angle of the loop are classified into low and high frequency regimes, separated by a transition frequency which is also a function of lithium diffusivity and grain size, fT = D/l₂. Research shows that the crystallographic orientation of the surface actuated grain has a significant impact on the shape of the loop. The polycrystalline crystallographic orientation of the grains induces a diffusion path network in the electrode which impacts on the mechanical reliability of the battery. Simulations demonstrate that continuous batterymore » cycling results in a cumulative capacity loss as a result of the hysteric non-reversible lithium intercalation. Furthermore, results suggest that ESM has the capability to infer the local out-of-plane lithium diffusivity and the out-of-plane contribution to Vegard tensor.« less

Authors:
 [1];  [2];  [2];  [1]
  1. Purdue Univ., West Lafayette, IN (United States). School of Materials Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1065761
DOE Contract Number:  
ERKCC61
Resource Type:
Journal Article
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 158; Journal Issue: 10; Related Information: FIRST partners with Oak Ridge National Laboratory (lead); Argonne National Laboratory; Drexel University; Georgia State University; Northwestern University; Pennsylvania State University; Suffolk University; Vanderbilt University; University of Virginia; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous), solar (fuels), energy storage (including batteries and capacitors), hydrogen and fuel cells, electrodes - solar, mechanical behavior, charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Chung, Ding-Wen, Balke, Nina, Kalinin, Sergei V., and Edwin Garcia, R. Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films. United States: N. p., 2011. Web. doi:10.1149/1.3619775.
Chung, Ding-Wen, Balke, Nina, Kalinin, Sergei V., & Edwin Garcia, R. Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films. United States. https://doi.org/10.1149/1.3619775
Chung, Ding-Wen, Balke, Nina, Kalinin, Sergei V., and Edwin Garcia, R. 2011. "Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films". United States. https://doi.org/10.1149/1.3619775.
@article{osti_1065761,
title = {Virtual Electrochemical Strain Microscopy of Polycrystalline LiCoO2 Films},
author = {Chung, Ding-Wen and Balke, Nina and Kalinin, Sergei V. and Edwin Garcia, R.},
abstractNote = {A recently developed technique, electrochemical strain microscopy (ESM), utilizes the strong coupling between ionic current and anisotropic volumetric chemical expansion of lithium-ion electrode materials to dynamically probe the sub-one-hundred? nm inter-facial kinetic intercalation properties. A numerical technique based on the finite element method was developed to analyze the underlying physics that govern the ESM signal generation and establish relations to battery performance. The performed analysis demonstrates that the diffusion path within a thin film is tortuous and the extent of lithium diffusion into the electrode is dependent on the SPM-tip-imposed overpotential frequency. The detected surface actuation gives rise to the development of an electromechanical hysteresis loop whose shape is dependent on grain size and overpotential frequency. Shape and tilting angle of the loop are classified into low and high frequency regimes, separated by a transition frequency which is also a function of lithium diffusivity and grain size, fT = D/l₂. Research shows that the crystallographic orientation of the surface actuated grain has a significant impact on the shape of the loop. The polycrystalline crystallographic orientation of the grains induces a diffusion path network in the electrode which impacts on the mechanical reliability of the battery. Simulations demonstrate that continuous battery cycling results in a cumulative capacity loss as a result of the hysteric non-reversible lithium intercalation. Furthermore, results suggest that ESM has the capability to infer the local out-of-plane lithium diffusivity and the out-of-plane contribution to Vegard tensor.},
doi = {10.1149/1.3619775},
url = {https://www.osti.gov/biblio/1065761}, journal = {Journal of the Electrochemical Society},
issn = {0013-4651},
number = 10,
volume = 158,
place = {United States},
year = {Wed Aug 03 00:00:00 EDT 2011},
month = {Wed Aug 03 00:00:00 EDT 2011}
}