Monitoring Redox Processes in Lithium-Ion Batteries by Laboratory-Scale Operando X-ray Emission Spectroscopy

Krishnan, Abiram; Lee, Dong-Chan; Slagle, Ian; Ahsan, Sumaiyatul; Mitra, Samantha; Read, Ethan; Alamgir, Faisal M.

doi:10.1021/acsami.3c18424

Title: Monitoring Redox Processes in Lithium-Ion Batteries by Laboratory-Scale Operando X-ray Emission Spectroscopy

Journal Article · 19 March 2024 · ACS Applied Materials and Interfaces

DOI: https://doi.org/10.1021/acsami.3c18424 · OSTI ID:2469577

^[1];

^[2]; Slagle, Ian ^[1];

^[1]; Mitra, Samantha ^[1]; Read, Ethan ^[1]; Alamgir, Faisal M. ^[1]

Georgia Institute of Technology, Atlanta, GA (United States)
Georgia Institute of Technology, Atlanta, GA (United States); Hongik University, Seoul (Korea, Republic of)

Tracking changes in the chemical state of transition metals in alkali-ion batteries is crucial to understanding the redox chemistry during operation. X-ray absorption spectroscopy (XAS) is often used to follow the chemistry through observed changes in the chemical state and local atomic structure as a function of the state-of-charge (SoC) in batteries. In this study, we utilize an operando X-ray emission spectroscopy (XES) method to observe changes in the chemical state of active elements in batteries during operation. Operando XES and XAS were compared by using a laboratory-scale setup for four different battery systems: LiCoO₂ (LCO), Li[Ni_1/3Co_1/3Mn_1/3]O₂ (NMC111), Li[Ni_0.8Co_0.1Mn_0.1]O₂ (NMC811), and LiFePO₄ (LFP) under a constant current charging the battery in 10 h (C/10 charge rate). We show that XES, despite narrower chemical shifts in comparison to XAS, allows us to fingerprint the battery SOC in real time. We further demonstrate that XES can be used to track the change in net spin of the probed atoms by analyzing changes in the emission peak shape. As a test case, the connection between net spin and the local chemical and structural environment was investigated by using XES and XAS in the case of electrochemically delithiated LCO in the range of 2–10% lithium removal.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2469577

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 13 Vol. 16; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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25 ENERGY STORAGE
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Title: Monitoring Redox Processes in Lithium-Ion Batteries by Laboratory-Scale Operando X-ray Emission Spectroscopy

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