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Title: In Situ Potentiodynamic Analysis of the Electrolyte/Silicon Electrodes Interface Reactions - A Sum Frequency Generation Vibrational Spectroscopy Study

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.5b10333· OSTI ID:1379048
 [1];  [2];  [2];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
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The key factor in long-term use of batteries is the formation of an electrically insulating solid layer that allows lithium ion transport but stops further electrolyte redox reactions on the electrode surface, hence solid electrolyte interphase (SEI). In this paper, we have studied a common electrolyte, 1.0 M LiPF6/ethylene carbonate (EC)/diethyl carbonate (DEC), reduction products on crystalline silicon (Si) electrodes in a lithium (Li) half-cell system under reaction conditions. We employed in situ sum frequency generation vibrational spectroscopy (SFG-VS) with interface sensitivity in order to probe the molecular composition of the SEI surface species under various applied potentials where electrolyte reduction is expected. We found that, with a Si(100)-hydrogen terminated wafer, a Si-ethoxy (Si-OC2H5) surface intermediate forms due to DEC decomposition. Our results suggest that the SEI surface composition varies depending on the termination of Si surface, i.e., the acidity of the Si surface. We provide the evidence of specific chemical composition of the SEI on the anode surface under reaction conditions. This supports an electrochemical electrolyte reduction mechanism in which the reduction of the DEC molecule to an ethoxy moiety plays a key role. Finally, these findings shed new light on the formation mechanism of SEI on Si anodes in particular and on SEI formation in general.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1379048
Journal Information:
Journal of the American Chemical Society, Vol. 138, Issue 3; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 75 works
Citation information provided by
Web of Science

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Cited By (5)

Reductive reactions via excess Li in mixture electrolytes of Li ion batteries: an ab initio molecular dynamics study journal January 2019
Vibrational sum-frequency generation spectroscopy of electrode surfaces: studying the mechanisms of sustainable fuel generation and utilisation journal January 2019
In situ observation of the potential-dependent structure of an electrolyte/electrode interface by heterodyne-detected vibrational sum frequency generation journal January 2020
Designing superior solid electrolyte interfaces on silicon anodes for high-performance lithium-ion batteries journal January 2019
Recent Progress in Advanced Characterization Methods for Silicon‐Based Lithium‐Ion Batteries journal May 2019

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