Magnetic susceptibility measurements on Li-intercalated graphite: Paramagnetic to diamagnetic transitions in C12Li induced by magnetic field

Mukai, Kazuhiko; Inoue, Takao

doi:10.1016/j.carbon.2017.08.012

Cited by 15 publications

(9 citation statements)

References 31 publications

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“…A high diamagnetic susceptibility of pure graphite is known to result in local magnetic fields, which, in general, act as demagnetizing fields and cause mismatch in the resonance condition, yielding shift and inhomogeneous broadening of NMR spectra . Weakening or destroying the diamagnetic property upon insertion of intercalants into graphite has been reported in the literature. − Thus, Li insertion is expected to minimize the effect of demagnetizing fields and enhance the field homogeneity, resulting in improvement of NMR spectral resolution. This could also explain the less pronounced changes in the Na-ion cells because sodium atoms are unable to enter the graphitic interlayer with the electrolyte solvent used in our work and hence to influence significantly the diamagnetic property.…”

Section: Discussionmentioning

confidence: 99%

“…Graphite is a well-known material with a quasi-two-dimensional structure and highly anisotropic properties. Graphite functionalization including metal decoration, doping, intercalation, and hybridization has been intensively studied in the last decades. , Intercalation of organic and inorganic species into graphite has attracted great attention due to a variety of unique electronic properties ranging from magnetism to superconductivity. − Whereas graphite is known to be an anomalous diamagnetic material with a highly anisotropic susceptibility, its large diamagnetism has been found to decrease when graphite is doped or intercalated. , Mukai and Inoue have observed paramagnetic to diamagnetic transition induced by the field in Li-intercalated graphite at 300 K and suggested the compounds with a certain intercalation degree to be applicable for switching devices . Weakening or destroying the diamagnetic property upon graphite intercalation has been explained by geometric factors, such as the stacking sequence and the repeated distance along the c -axis, and by a shift of the Fermi level outside the degeneracy region, following charge transfer.…”

Section: Introductionmentioning

confidence: 99%

“…6,7 Mukai and Inoue have observed paramagnetic to diamagnetic transition induced by the field in Li-intercalated graphite at 300 K and suggested the compounds with a certain intercalation degree to be applicable for switching devices. 8 Weakening or destroying the diamagnetic property upon graphite intercalation has been explained by geometric factors, such as the stacking sequence and the repeated distance along the c-axis, and by a shift of the Fermi level outside the degeneracy region, following charge transfer.…”

Section: ■ Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Effect of Charge Transfer upon Li- and Na-Ion Insertion in Fine-Grained Graphitic Material as Probed by NMR

Vyalikh

Koroteev

Münchgesang

et al. 2019

ACS Appl. Mater. Interfaces

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We investigated the insertion−extraction behaviors of Li and Na ions in graphitic materials using solidstate NMR. A unique advantage of high-degree 13 C-isotope enrichment of graphitic material allowed sensitive and metastable graphite intercalation compounds to be measured in a short time. Ex situ 13 C magic-angle spinning NMR spectra of 13 C fine-grained graphite are presented as a function of state-of-charge. The observations are discussed with respect to graphite intercalation phenomena, which include the effects of charge transfer and the demagnetizing field. Dramatic narrowing of the 13 C NMR signal in metal-intercalated graphite evidences quasi-complete charge transfer occurring between lithium and graphite host material and resulting in reducing the macroscopic field effects. Upon Na insertion, incomplete charge transfer is observed and explained by inaccessibility of graphitic interlayer space for Na ions in our study. In addition, critical issues of reversibility of Li-and Na-ion electrochemical cells and solid electrolyte interphase formation are considered on the atomic scale. The knowledge gained in the present work can be applied to advanced high-power-density electrode materials for safe and fast-charging metal-ion batteries or for novel spintronic concepts with controlled spin-polarized charge carrier injection and transport combined with the possibility to manipulate magnetic anisotropy.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Effect of Charge Transfer upon Li- and Na-Ion Insertion in Fine-Grained Graphitic Material as Probed by NMR

Vyalikh

Koroteev

Münchgesang

et al. 2019

ACS Appl. Mater. Interfaces

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“…Shortly after the beginning of discharging (at a SOC of about 93%), the peak centers of both signals shifted by approximately 300 Hz (2 ppm). During lithiation of the graphite electrode the transition of diamagnetic to paramagnetic graphite takes place 71 . The corresponding susceptibility changes could be the reason for the center frequency shifts.…”

Section: Long-run In-operando Nmr Of the Lithium Microstructure Forma...mentioning

confidence: 99%

Long-run in operando NMR to investigate the evolution and degradation of battery cells

Kayser

Mester

Mertens

et al. 2018

Phys. Chem. Chem. Phys.

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To improve the lifetime of lithium-ion batteries, a detailed understanding of the degradation mechanisms is essential. Nuclear magnetic resonance (NMR) is able to unravel the reversible as well as irreversible transient changes of composition, shape and morphology in a battery cell. Using a newly developed cylindrical battery container free of metallic components in combination with a numerically optimized saddle coil, in operando NMR investigations of battery cells over hundreds of charge/discharge cycles are presented. Alternating with NMR data acquisition, electrochemical impedance spectra (EIS) can be recorded, which enables correlative analysis of the two techniques. Long-run in operando NMR measurements on a Li metal vs. graphite cell reveal the formation and evolution of mossy and dendritic Li microstructures over a period of 1000 h, which illustrates the capabilities of NMR to identify dendrite mitigation strategies in cells operated under realistic conditions.

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“…The sample where x = 0 (pure graphite) showed a large diamagnetic response with magnetic susceptibility values at 5 K and 300 K being À127 3 10 À6 emu$mol À1 and -67 3 10 À6 emu$mol À1 , respectively. The transition from diamagnetic to paramagnetic behavior took place gradually at around x R 0.34, which contradicts the expected x dependence of the orbital magnetic susceptibility based on the tight binding model (Mukai and Inoue, 2017).…”

Section: Magnetic Properties Of Active Materialsmentioning

confidence: 58%

Magnetically active lithium-ion batteries towards battery performance improvement

et al. 2021

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Lithium-ion batteries (LIBs) are currently the fastest growing segment of the global battery market, and the preferred electrochemical energy storage system for portable applications. Magnetism is one of the forces that can be applied improve performance, since the application of magnetic fields influences electrochemical reactions through variation of electrolyte properties, mass transportation, electrode kinetics, and deposits morphology. This review provides a description of the magnetic forces present in electrochemical reactions and focuses on how those forces may be taken advantage of to influence the LIBs components (electrolyte, electrodes, and active materials), improving battery performance. The different ways that magnetic forces can interact with LIBs components are discussed, as well as their influence on the electrochemical behavior. The suitable control of these forces and interactions can lead to higher performance LIBs structures and to the development of innovative concepts.

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Magnetic susceptibility measurements on Li-intercalated graphite: Paramagnetic to diamagnetic transitions in C12Li induced by magnetic field

Cited by 15 publications

References 31 publications

Effect of Charge Transfer upon Li- and Na-Ion Insertion in Fine-Grained Graphitic Material as Probed by NMR

Effect of Charge Transfer upon Li- and Na-Ion Insertion in Fine-Grained Graphitic Material as Probed by NMR

Long-run in operando NMR to investigate the evolution and degradation of battery cells

Magnetically active lithium-ion batteries towards battery performance improvement

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