Redox oscillations in 18650-type lithium-ion cell revealed by <i>in operando</i> Compton scattering imaging

Suzuki, Kosuke; Suzuki, Shunta; Otsuka, Yuji; Tsuji, Naruki; Jalkanen, Kirsi; Koskinen, Jari; Hoshi, Kazushi; Honkanen, A.; Hafiz, Hasnain; Sakurai, Y.; Kanninen, Mika; Huotari, Simo; Bansil, Arun; Sakurai, Hiroshi; Barbiellini, B.

doi:10.1063/5.0048310

Cited by 6 publications

(4 citation statements)

References 28 publications

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“…However, in the case of the discharged battery (x = 1.0), the positron spillover increases and the lifetime for the bulklike state is about 30 ps higher than the calculated bulk value. Since the intensity of the positron surface states is high both for x = 1 and x = 0.5, this state could in principle be used to monitor in operando non-homogeneous lithiation states at the grain boundaries of the cathode [50]. Therefore, one could detect possible lithium bottlenecks at the grain-graphite interface.…”

Section: Discussionmentioning

confidence: 99%

Positron Annihilation Spectroscopy as a Diagnostic Tool for the Study of LiCoO2 Cathode of Lithium-Ion Batteries

et al. 2021

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Positron annihilation spectroscopy using lifetime and Doppler broadening allows the characterization of the lithiation state in LiCoO2 thin film used in cathode of lithium-ion batteries. The lifetime results reflect positron spillover because of the presence of graphite in between the oxide grains in real cathode Li-ion batteries. This spillover produces an effect in the measured positron parameters which are sensitive to delocalized electrons from lithium atoms as in Compton scattering results. The first component of the positron lifetime corresponds to a bulk-like state and can be used to characterize the state of charge of the cathode while the second component represents a surface state at the grain-graphite interface.

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Section: Discussionmentioning

confidence: 99%

Positron Annihilation Spectroscopy as a Diagnostic Tool for the Study of LiCoO2 Cathode of Lithium-Ion Batteries

et al. 2021

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“…The present method thus provides an in operando visualization of Li concentration in a closed cell and enables identification of the mechanism of cell degradation. This approach has been used for several commercial batteries [37][38][39][40]61].…”

Section: Case Study 1: Lithium Distribution In Commercial Libsmentioning

confidence: 99%

Identifying Redox Orbitals and Defects in Lithium-Ion Cathodes with Compton Scattering and Positron Annihilation Spectroscopies: A Review

et al. 2022

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Reduction-oxidation (redox) reactions that transfer conduction electrons from the anode to the cathode are the fundamental processes responsible for generating power in Li-ion batteries. Electronic and microstructural features of the cathode material are controlled by the nature of the redox orbitals and how they respond to Li intercalation. Thus, redox orbitals play a key role in performance of the battery and its degradation with cycling. We unravel spectroscopic descriptors that can be used to gain an atomic-scale handle on the redox mechanisms underlying Li-ion batteries. Our focus is on X-ray Compton Scattering and Positron Annihilation spectroscopies and the related computational approaches for the purpose of identifying orbitals involved in electrochemical transformations in the cathode. This review provides insight into the workings of lithium-ion batteries and opens a pathway for rational design of next-generation battery materials.

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“…Moreover, the imaging Compton technique has been applied to in operando and in situ measurements to monitor the lithiation state of commercial batteries, see Ref. [8] and references therein. There are fundamental difficulties in visualizing redox orbitals using X-ray photoemission spectroscopy (XPS) [9], soft X-ray absorption (XAS) [10], and X-ray resonant inelastic scattering (RIXS) [11] since these techniques are surface sensitive.…”

Section: Introductionmentioning

confidence: 99%

Magnetic Compton Scattering Study of Li-Rich Battery Materials

et al. 2021

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The redox process in a lithium-ion battery occurs when a conduction electron from the lithium anode is transferred to the redox orbital of the cathode. Understanding the nature of orbitals involved in anionic as well as cationic redox reactions is important for improving the capacity and energy density of Li-ion batteries. In this connection, we have obtained magnetic Compton profiles (MCPs) from the Li-rich cation-disordered rock-salt compound LixTi0.4Mn0.4O2 (LTMO). The MCPs, which involved the scattering of circularly polarized hard X-rays, are given by the momentum density of all the unpaired spins in the material. The net magnetic moment in the ground state can be extracted from the area under the MCP, along with a SQUID measurement. Our analysis gives insight into the role of Mn 3d magnetic electrons and O 2p holes in the magnetic redox properties of LTMO.

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Redox oscillations in 18650-type lithium-ion cell revealed by in operando Compton scattering imaging

Cited by 6 publications

References 28 publications

Positron Annihilation Spectroscopy as a Diagnostic Tool for the Study of LiCoO2 Cathode of Lithium-Ion Batteries

Positron Annihilation Spectroscopy as a Diagnostic Tool for the Study of LiCoO2 Cathode of Lithium-Ion Batteries

Identifying Redox Orbitals and Defects in Lithium-Ion Cathodes with Compton Scattering and Positron Annihilation Spectroscopies: A Review

Magnetic Compton Scattering Study of Li-Rich Battery Materials

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