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

Anastasia Vyalikh; Victor O Koroteev; Wolfram Münchgesang; Thomas Köhler; Christian Röder; Erica Brendler; Alexander V Okotrub; Lyubov G Bulusheva; Dirk C Meyer

doi:10.1021/acsami.8b20115

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

ACS Appl Mater Interfaces. 2019 Mar 6;11(9):9291-9300. doi: 10.1021/acsami.8b20115. Epub 2019 Feb 21.

Authors

Affiliations

¹ Institut für Experimentelle Physik , Technische Universität Bergakademie Freiberg , Leipziger Str. 23 , 09599 Freiberg , Germany.
² Nikolaev Institute of Inorganic Chemistry , SB RAS , 3 Acad. Lavrentiev Avenue , 630090 Novosibirsk , Russia.
³ Institut für Theoretische Physik , Technische Universität Bergakademie Freiberg , Leipziger Str. 23 , 09596 Freiberg , Germany.
⁴ Institut für Analytische Chemie , Technische Universität Bergakademie Freiberg , Leipziger Str. 29 , 09599 Freiberg , Germany.
⁵ Novosibirsk State University , 2 Pirogova Str. , 630090 Novosibirsk , Russia.

PMID: 30741532
DOI: 10.1021/acsami.8b20115

Abstract

We investigated the insertion-extraction behaviors of Li and Na ions in graphitic materials using solid-state NMR. A unique advantage of high-degree ¹³C-isotope enrichment of graphitic material allowed sensitive and metastable graphite intercalation compounds to be measured in a short time. Ex situ ¹³C magic-angle spinning NMR spectra of ¹³C 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 ¹³C 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.

Keywords: 13C solid-state NMR; 13C-enriched graphite; EPR; Raman spectroscopy; fine-grained graphitic material; lithium intercalation; sodium intercalation.