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Title: Understanding the Origin of the Nonpassivating Behavior of Si-Based Anodes during the Initial Cycles

Journal Article · · Journal of Physical Chemistry C
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In this contribution, we combined electrochemical cycling and X-ray photoelectron spectroscopy (XPS) to understand the nonpassivating behavior of the solid electrolyte interphase (SEI) on Si anodes during the first cycles. Based on galvanostatic measurements, we show that the irreversible capacity loss is reduced after the first cycle, and it stays almost constant from the second cycle onwards. XPS was used to determine the root causes of the Coulombic inefficiency, showing that the rate of decomposition of the organic solvents strongly decreased after the first cycle, whereas the rate of salt decomposition is almost unchanged between cycles. We determine that the inhibition of the decomposition reaction of the organic solvent is responsible for the lower Coulombic loss during the second electrochemical cycle in comparison to the first, whereas the nonpassivating behavior toward the salt decomposition is one of the main causes of capacity loss upon cycling. We further revisit the role of cracking in contributing to capacity loss. Whereas high volumetric expansion remains an issue plaguing the performance of Si anodes, our chronoamperometry studies reveal that the SEI formed on Si anodes does not passivate even when the electrode is fully expanded, and no additional surface is exposed. Overall, our work establishes the need to address the chemical and electrochemical instability of the SEI on the Si anode in addition to the more notorious issue of cracking.

Research Organization:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V), Silicon Electrolyte Interface Stabilization (SEISta) Consortium
DOE Contract Number:
AC36-08GO28308
OSTI ID:
1888772
Report Number(s):
NREL/JA-5K00-84052; MainId:84825; UUID:c6cfc067-0565-40c0-9dd5-4dbdaf00adab; MainAdminID:67523
Journal Information:
Journal of Physical Chemistry C, Vol. 126, Issue 33
Country of Publication:
United States
Language:
English

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INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
electrochemical cycling
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Si anodes
solid electrolyte interphase
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