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1930511
Shivakumar Samanta
5PSEco

Journal Article Synopsis

Journal Name:
Synchronized Operando Analysis of Graphite Negative Electrode of LiIon Battery.

Authors:
Hiroyuki Fujimoto, Miwa Murakami, Toshiro Yamanaka, Keiji Shimoda, Hisao Kiuchi, Zempachi
Ogumi, and Takeshi Abe

Journal:
Journal of The Electrochemical Society

Introduction
It's been about 30 years since graphite negative electrode materials were first
commercialised for lithium-ion batteries. The charge/discharge method, however, has yet to be
determined. The production of a Li-graphite intercalation compound is the basic negative
electrode reaction process (Li-GIC). Li ions initially intercalate into each graphite interlayer to
generate dilute stage 1. This stage then transitions to a higher stage structure. We provide a
synchronised operando analysis idea combining SXD, 7 Li-NMR, and Raman spectroscopy and
perform the proposed analysis for the graphite electrode of a Li-ion battery to corroborate this
charge/discharge reaction process.

Experiment
Three types of half-cells comprised of graphite and Li-metal electrodes were built with an
electrolyte of 1 moldm3 LiPF6/ethylene carbonate + ethyl methyl carbonate to perform operando
measurements utilising SXD, Li-NMR, and Raman spectroscopy. In an Ar-filled glovebox, the
cells were built. Before the operando measurement, the cells were charged and discharged in
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advance within the potential range of 0.01 to 2.5 V at a current rate of around 0.1 C. The
graphite electrode was positive in this cell arrangement because the Li was used as a counter
electrode. For consistency with practical full-cell-type rechargeable Li-ion batteries, we refer to
Li intercalation into graphite as "charging" and Li deintercalation as "discharging." Then, in the
range of 0.01 to 2.5 V, SXD, 7 Li-NMR, and Raman measurements were done at a current rate
of 0.1 CA (for 10 hours).

Results and discussion

The 7 Li-NMR chemical shifts, as well as the d100 and d002 values, fluctuate as a
function of x in LiCx. Peaks A and B were found at x > 22 at = 5–15 ppm and at x 22 at = 40–45
ppm, respectively, in the 7 Li-NMR findings; the former shifted towards higher magnetic fields as
the Li concentration declined. Within the LiC72.0–LiC63.0 composition range, the 101 diffraction
intensity rapidly declined and almost vanished as intercalation progressed. When the LiC63.0
composition was obtained, the graphite AB stacking was changed into AA stacking, indicating
that Li species had intercalated into all interlayers.
As a result, a diluted stage 1 was created. In the LiC72.0–LiC63.0 range, the 002
diffraction strength declined as the d value climbed steadily from 0.3354 nm to 0.34 nm, and the
002 peak ultimately separated into a distinct doublet. The vibration modes on both graphene
sheet types alter dramatically as a result, and E2g2 breaks into two bands, corresponding to the
E0 2g2 (GL-band) and 2g2 (GH-band) vibration modes. 5,29–32 The former shows up with a
lesser frequency than the latter.
The Daumas-Hérold model then converts stage 8 molecules into lower stage
compounds in order from stage 7 to stage 6 to stage 5 to stage 4. The GL-band changes
towards a lower frequency side than the G-band for an alkali metal-GIC, according to Solin; this
fact is also compatible with their findings. The dynamic shift in the Raman spectra was similarly
in good agreement with the SXD profile changes.

Conclusions
In a Liion battery, we used SXD, 7 Li-NMR, and Raman spectroscopy to do an operando
investigation of the graphite electrode charge/discharge mechanism. During the process, the
spectra of graphite electrodes were measured one by one. The charge/discharge curves were
used to estimate the x composition in LiCx, which was analysed synchronously with the
operando dataset. The most essential part of this research is the presentation of a technique for
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simultaneously tracking changes in SXD, 7 Li-NMR, and Raman spectra with changes in LiCx
composition.
Due to structural changes during charge/discharge events, this offers information
regarding C–C bond vibration mode behaviour and interactions between Li and carbon atoms.
The 002 diffraction and the G-band of graphite shifted from singlet to doublet forms around
LiC72, according to synchronised investigation utilising SXD and Raman spectroscopy. This
suggests that the saturation composition of the dilute stage 1 is LiC72, and it was determined
that Li rearrangement between the interlayers leads to stage 7 via stage 8. The shift from LiC9n
to LiC6n occurs near LiC21–22, according to a synchronised analysis of SXD and 7 Li-NMR
spectroscopic results. The intercalation mechanism seen in Fig. 1 can be described decisively
since the 7 Li-NMR and Raman measurements show very excellent agreement with the SXD
observations.

Acknowledgments
The New Energy and Industrial Technology Development Organization and the
Research and Development Innovative for Scientific Innovation of New Generation Battery 2
(RISING2) project provided funding for this research.
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References
A. Hérold and B. Soc, Chim. France, 187, 999 (1955)
Hiroyuki Fujimoto et al 2021 J. Electrochem. Soc. 168 080508
D. Guerard and A. Hérold, Carbon, 13, 337 (1975).