TY - JOUR

T1 - Effect of Charge Transfer upon Li- and Na-Ion Insertion in Fine-Grained Graphitic Material as Probed by NMR

AU - Vyalikh, Anastasia

AU - Koroteev, Victor O.

AU - Münchgesang, Wolfram

AU - Köhler, Thomas

AU - Röder, Christian

AU - Brendler, Erica

AU - Okotrub, Alexander V.

AU - Bulusheva, Lyubov G.

AU - Meyer, Dirk C.

N1 - Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/3/6

Y1 - 2019/3/6

N2 - We investigated the insertion-extraction behaviors of Li and Na ions in graphitic materials using solid-state 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.

AB - We investigated the insertion-extraction behaviors of Li and Na ions in graphitic materials using solid-state 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.

KW - C solid-state NMR

KW - C-enriched graphite

KW - EPR

KW - fine-grained graphitic material

KW - lithium intercalation

KW - Raman spectroscopy

KW - sodium intercalation

KW - RAMAN-SPECTRA

KW - ELECTRON-SPIN-RESONANCE

KW - C-13-enriched graphite

KW - NUCLEAR-MAGNETIC-RESONANCE

KW - GRAPHENE

KW - STATE

KW - CARBONS

KW - DIAMAGNETISM

KW - C-13 solid-state NMR

KW - C-13 NMR

KW - LITHIUM

KW - ELECTROCHEMICAL INTERCALATION

UR - http://www.scopus.com/inward/record.url?scp=85062585450&partnerID=8YFLogxK

U2 - 10.1021/acsami.8b20115

DO - 10.1021/acsami.8b20115

M3 - Article

C2 - 30741532

AN - SCOPUS:85062585450

VL - 11

SP - 9291

EP - 9300

JO - ACS applied materials & interfaces

JF - ACS applied materials & interfaces

SN - 1944-8244

IS - 9

ER -