skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electrochemical Charge Transfer Reaction Kinetics at the Silicon-Liquid Electrolyte Interface

Abstract

Since the gravimetric lithiation capacity of silicon is roughly ten times that of graphite, while their mass densities are comparable, for the same particle size the current density required to cycle a silicon electrode at a given C-rate is about ten times greater than that of graphite. Depending on the magnitude of the corresponding Butler-Volmer exchange current density, j o, such high current densities may cause the charge transfer kinetics at the silicon-electrolyte interface to become rate limiting. Previously reported values of j o for Si differ by about 10 orders of magnitude. Here we report j o measurements using electrochemical impedance spectroscopy (EIS) for single crystal electronically conductive silicon wafers with well-defined (100) and (111) orientations and active surface areas. The electrochemical cycling regime was designed to avoid artifacts due to stress-induced surface cracking of Si upon lithiation. The exchange current density of the silicon-electrolyte interface is found to be 0.1 ± 0.01 mA/cm 2 when using electrolyte consisting of 1 M LiPF 6 in EC/DMC (1/1 by wt) + FEC (10 wt%) + VC (2 wt%). Furthermore, these results are then used to illustrate the dependence of kinetic overpotential on particle size and C-rate for silicon compared tomore » lower volumetric capacity compounds such as graphite.« less

Authors:
 [1];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Northeastern Center for Chemical Energy Storage (NECCES)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1387333
Grant/Contract Number:
SC0001294
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 162; Journal Issue: 13; Related Information: NECCES partners with Stony Brook University (lead); Argonne National Laboratory; Binghamton University; Brookhaven National University; University of California, San Diego; University of Cambridge, UK; Lawrence Berkeley National Laboratory; Massachusetts Institute of Technology; University of Michigan; Rutgers University; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; energy storage (including batteries and capacitors); defects; charge transport; materials and chemistry by design; synthesis (novel materials); Charge Transfer Reaction; Electrochemical Kinetics; Exchange Current Density; Lithium-Ion battery; Silicon Anode

Citation Formats

Swamy, Tushar, and Chiang, Yet -Ming. Electrochemical Charge Transfer Reaction Kinetics at the Silicon-Liquid Electrolyte Interface. United States: N. p., 2015. Web. doi:10.1149/2.0181513jes.
Swamy, Tushar, & Chiang, Yet -Ming. Electrochemical Charge Transfer Reaction Kinetics at the Silicon-Liquid Electrolyte Interface. United States. doi:10.1149/2.0181513jes.
Swamy, Tushar, and Chiang, Yet -Ming. Fri . "Electrochemical Charge Transfer Reaction Kinetics at the Silicon-Liquid Electrolyte Interface". United States. doi:10.1149/2.0181513jes. https://www.osti.gov/servlets/purl/1387333.
@article{osti_1387333,
title = {Electrochemical Charge Transfer Reaction Kinetics at the Silicon-Liquid Electrolyte Interface},
author = {Swamy, Tushar and Chiang, Yet -Ming},
abstractNote = {Since the gravimetric lithiation capacity of silicon is roughly ten times that of graphite, while their mass densities are comparable, for the same particle size the current density required to cycle a silicon electrode at a given C-rate is about ten times greater than that of graphite. Depending on the magnitude of the corresponding Butler-Volmer exchange current density, jo, such high current densities may cause the charge transfer kinetics at the silicon-electrolyte interface to become rate limiting. Previously reported values of jo for Si differ by about 10 orders of magnitude. Here we report jo measurements using electrochemical impedance spectroscopy (EIS) for single crystal electronically conductive silicon wafers with well-defined (100) and (111) orientations and active surface areas. The electrochemical cycling regime was designed to avoid artifacts due to stress-induced surface cracking of Si upon lithiation. The exchange current density of the silicon-electrolyte interface is found to be 0.1 ± 0.01 mA/cm2 when using electrolyte consisting of 1 M LiPF6 in EC/DMC (1/1 by wt) + FEC (10 wt%) + VC (2 wt%). Furthermore, these results are then used to illustrate the dependence of kinetic overpotential on particle size and C-rate for silicon compared to lower volumetric capacity compounds such as graphite.},
doi = {10.1149/2.0181513jes},
journal = {Journal of the Electrochemical Society},
number = 13,
volume = 162,
place = {United States},
year = {Fri Oct 02 00:00:00 EDT 2015},
month = {Fri Oct 02 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

Save / Share: