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Competition between Conversion Reaction with Cerium Dioxide and Lithium Plating in Superconcentrated Electrolyte
Tohru Shiga1, Yumi Masuoka1, Yuichi Kato1
1Toyota Central Research & Development Laboratories Inc., Yokomichi, Nagakute, Aichi-ken 480-1192, Japan.
Langmuir : the ACS Journal of Surfaces and Colloids
|November 11, 2020
Summary
In superconcentrated electrolytes, the conversion reaction of cerium dioxide (CeO2) was unexpectedly delayed after lithium plating, contrary to dilute electrolytes. This shift was attributed to the solid electrolyte interphase (SEI) on CeO2.
Area of Science:
- Materials Science
- Electrochemistry
- Battery Technology
Background:
- Cerium dioxide (CeO2) is explored as a conversion-type anode material for lithium-ion batteries.
- Understanding the electrochemical behavior of CeO2 in different electrolyte concentrations is crucial for battery performance.
- The solid electrolyte interphase (SEI) significantly influences electrode reactions and battery stability.
Purpose of the Study:
- To investigate the Li-ion insertion and conversion reaction mechanism of CeO2 in a superconcentrated electrolyte.
- To determine the effect of electrolyte concentration on the electrochemical sequence of CeO2 conversion and lithium plating/stripping.
- To elucidate the role of the solid electrolyte interphase (SEI) in altering the expected electrochemical behavior.
Main Methods:
- Electrochemical studies using a CeO2/copper composite electrode.
- Utilizing a superconcentrated electrolyte comprising lithium bis(fluorosulfonyl)amide (LiFSA) and methylphenylamino-di(trifluoroethyl) phosphate (PNMePh).
- Comparative analysis with a dilute LiFSA/PNMePh electrolyte.
- Characterization using Energy-Dispersive X-ray Spectroscopy (EDX) and Electrochemical Impedance Analysis (EIA).
Main Results:
- The conversion reaction of CeO2 was observed to occur after lithium plating in the superconcentrated electrolyte, reversing the expected order.
- This phenomenon was not observed in the dilute electrolyte, highlighting the impact of electrolyte concentration.
- EDX and EIA revealed that the SEI formed on CeO2 had different composition and higher interfacial resistance compared to the SEI on metallic lithium.
Conclusions:
- The SEI layer on CeO2 plays a critical role in dictating the electrochemical reaction sequence in superconcentrated electrolytes.
- The altered SEI properties in superconcentrated conditions lead to a delayed conversion reaction of CeO2.
- These findings are essential for designing advanced lithium-ion batteries with optimized electrode-electrolyte interfaces.
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