Probing the Formation of Cathode-Electrolyte Interphase on Lithium Iron Phosphate Cathodes via Operando Mechanical Measurements

Bal, Batuhan; Ozdogru, Bertan; Nguyen, Dan Thien; Li, Zheng; Murugesan, Vijayakumar; Capraz, Omer Ozgur

doi:10.1021/acsami.3c05749

Title: Probing the Formation of Cathode-Electrolyte Interphase on Lithium Iron Phosphate Cathodes via Operando Mechanical Measurements

Journal Article · Sat Sep 02 00:00:00 EDT 2023 · ACS Applied Materials & Interfaces

DOI:https://doi.org/10.1021/acsami.3c05749· OSTI ID:2203228

Bal, Batuhan; Ozdogru, Bertan; Nguyen, Dan Thien; Li, Zheng; Murugesan, Vijayakumar; Capraz, Omer Ozgur

Interfacial instabilities in electrodes control the performance and lifetime of Li-ion batteries. While the formation of the solid-electrolyte interphase (SEI) on anodes has received much attention, there is still a lack of understanding the formation of the cathode-electrolyte interphase (CEI) on the cathodes. To fill this gap, we report on dynamic deformations on LiFePO4 cathodes during charge/discharge by utilizing operando digital image correlation, impedance spectroscopy, and cryo X-ray photoelectron spectroscopy. LiFePO4 cathodes were cycled in either LiPF6, LiClO4, or LiTFSI-containing organic liquid electrolytes. Beyond the first cycle, Li-ion intercalation results in a nearly linear correlation between electrochemical strains and the state of (dis)-charge, regardless of the electrolyte chemistry. However, during the first charge in the LiPF6-containing electrolyte, there is a distinct irreversible positive strain evolution at the onset of anodic current rise as well as current decay at around 4.0 V. Impedance studies show an increase in surface resistance in the same potential window, suggesting the formation of CEI layers on the cathode. The chemistry of the CEI layer was characterized by X-ray photoelectron spectroscopy. LiF is detected in the CEI layer starting as early as 3.4 V and LixPOyFz appeared at voltages higher than 4.0 V during the first charge. Our approach offers insights into the formation mechanism of CEI layers on the cathode electrodes, which is crucial for the development of robust cathodes and electrolyte chemistries for higher-performance batteries.

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 2203228

Report Number(s):: NREL/JA-5700-87815; MainId:88590; UUID:d39d5203-149e-40fc-80b3-3966ffa99a32; MainAdminID:70903

Journal Information:: ACS Applied Materials & Interfaces, Vol. 15, Issue 36

Country of Publication:: United States

Language:: English

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Title: Probing the Formation of Cathode-Electrolyte Interphase on Lithium Iron Phosphate Cathodes via Operando Mechanical Measurements

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