Journal of Molecular Structure 1069 (2014) 157163

Contents lists available at ScienceDirect

Journal of Molecular Structure

journal homepage: www.elsevier.com/locate/molstruc

Investigation of solid electrolyte interface (SEI) lm on LiCoO2 cathode in

uoroethylene carbonate (FEC)-containing electrolyte by 2D correlation
X-ray photoelectron spectroscopy (XPS)
Yeonju Park a, Su Hyun Shin a, Hoon Hwang a, Sung Man Lee b, Sung Phil Kim c, Hyun Chul Choi c,,
Young Mee Jung a,
a

Department of Chemistry, and Institute for Molecular Science and Fusion Technology, Kangwon National University, Chunchon 200-701, Republic of Korea
Department of Advanced Materials Science & Engineering, Kangwon National University, Chunchon 200-701, Republic of Korea
c
Department of Chemistry, Chonnam National University, Gwangju 500-757, Republic of Korea
b

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Effect of uoroethylene carbonate

(FEC) on the electrochemical

performance of the LiCoO2 cathode.
 Solid electrolyte interface (SEI) lm
formation on the LiCoO2 cathode
during overcharge state.
 Reduced electrode/electrolyte
interfacial impedance in FEC additive
electrode.
 Mechanism of the electrochemical
reaction at the electrode/electrolyte
interface.

a r t i c l e

i n f o

Article history:
Available online 23 January 2014
Keywords:
Lithium-ion battery
2D correlation spectroscopy
Solid electrolyte interface (SEI)
X-ray photoelectron spectroscopy
Electrochemical impedance spectrum (EIS)
analysis

a b s t r a c t
The effects of uoroethylene carbonate (FEC) on the electrochemical performance of the LiCoO2 cathode
were investigated by galvanostatic chargedischarge testing and cyclic voltammetry (CV). It was found
that FEC has a positive effect on cycling stability and also improves cell performance. We also studied
solid electrolyte interface (SEI) lm on the LiCoO2 cathode, using X-ray photoelectron spectroscopy
(XPS) and 2D correlation spectroscopy. The 2D correlation XPS spectra showed that, initially, the polyvinylidene uoride (PVdF) binder and electrolyte components are decomposed, after which SEI components are formed on the LiCoO2 cathode surface. In the FEC-containing electrolyte, the polycarbonate
components are more abundant than in the FEC-free electrolyte. The formed carbonates in SEI lm can
act as Li+-conducting materials in reducing the electrode/electrolyte interfacial impedance. This hypothesis is supported by the results of an electrochemical impedance spectrum (EIS) analysis.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Rechargeable lithium-ion (Li-ion) batteries, owing to their high
density, high capacity, light weight, and other relevant properties,
Corresponding authors. Tel.: +82 62 530 3491; fax: +82 62 530 3389 (H.C. Choi).
Tel.: +82 33 250 8495; fax: +82 33 259 5667 (Y.M. Jung).
E-mail addresses: chc12@chonnam.ac.kr (H.C. Choi), ymjung@kanwon.ac.kr
(Y.M. Jung).
0022-2860/$ - see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molstruc.2014.01.041

have been widely used for energy storage. Recently, their application, hitherto limited to portable electronic devices, has been
extended to electric vehicles (EV) and hybrid electric vehicles
(HEV). Improvement of their safety as well as high power density,
therefore, has become a priority. Crucial in these regards is the
solid electrolyte interface (SEI) lm that is formed on battery electrode surfaces due to electrolyte decomposition during the initial
chargedischarge processes [1,2]. Many investigations on SEI have

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Y. Park et al. / Journal of Molecular Structure 1069 (2014) 157163

been conducted using, for example, ionic liquids [3,4] and

electrolyte additives [510] to improve Li-ion battery safety and
performance. Additionally, various analytical methods such as
ac-impedance, Fourier-transform infrared (FTIR) spectroscopy
and X-ray photoelectron spectroscopy (XPS) have been applied to
investigations of the composition and formation mechanism of
SEI lm [1119]. However, the reactions involved are very complicated, and are still not well understood.
Recently, uoroethylene carbonate (FEC) has attracted interest
as an SEI-formation additive for improved Li-ion battery cycle
performance at room temperature [2026]. The enhanced cycle
performance thus achieved can be ascribed to the FEC-additives
effected formation of thinner SEI lm that decreases electrode/
electrolyte interfacial impedance. Until now, most FEC study has
focused on the anode electrode, whereas the effect of FEC on the
cathode performance has been signicantly less examined. One
reason for this relative neglect is the fact that charged cathode
particles are covered not only with electrolyte components but also
organic/inorganic compounds such as lithium carbonate (Li2CO3),
lithium oxide (Li2O), lithium hydroxide (LiOH), lithium uoride
(LiF), and polycarbonate; discrimination of the many surface reactions in the obtained data, therefore, tends to be very difcult.
Generalized 2D correlation spectroscopy has attracted a high level of interest in the analytical science community for its considerable utility in many elds. 2D correlation spectra are calculated
from the dynamic spectra obtained by external perturbation-based
spectral measurement. This analytical technology has various
advantages including spectral resolution enhancement, the establishment of unambiguous assignments, and the capacity to determine, thereby, the sequence of spectral peaks emergence (for
additional details, see Refs. [2729]). As such, 2D correlation

spectroscopy is indispensable to the characterization of electrode

materials [3035]. In the present study, using ac-impedance
and XPS, we investigated the SEI on the LiCoO2 electrode in
FEC-containing electrolyte as a function of increasing charging
voltage; further, we applied 2D correlation spectroscopy to the
XPS spectra of the electrode in order to obtain detailed information
on the composition and structure of the SEI on the cathode.
2. Experimental section
The electrochemical behavior of LiCoO2 was investigated using
coin cells (2016 type). Slurries consisting of 95 wt% LiCoO2 (Nippon
Chemical Co.) powder, 3 wt% acetylene black, and 2 wt% polyvinylidene uoride (PVdF) dissolved in 1-methyl-2-pyrrolidinone were
prepared. Cathodes were formed by coating the slurry onto an aluminum foil substrate. Using these electrodes, test cells were fabricated, along with metallic Li anodes and polypropylene separators
(Celgard 2400) in a glove box lled with Ar gas. The electrolyte
used in this study was a 1.0 M solution of LiPF6 in ethylene carbonate-diethyl carbonate (EC:DEC = 1:1 by volume) without or with
1.0 wt% FEC (PANAX ETEC Co.). Subsequently, the test cells were
aged for 4 h at 40 C in a vacuum oven. Cell performance was evaluated by galvanostatically charging and discharging the cell within
the 3.04.5 V range at a constant current density of 0.2 C-rate at
room temperature with a WBCS 3000 battery tester system (Won
A Tech Corp, Korea). For the purposes of the evaluation, the term
charge referred to lithium extraction from LiCoO2, and the term
discharge, to lithium insertion into delithiated LiCoO2.
The cyclic voltammetry (CV) of a LiCoO2/Li half-cell was measured by PARSTAT 2273 (Princeton, USA). CV was performed at a
scan rate of 0.1 mV s1 at room temperature. The electrochemical

Fig. 1. Charge and discharge proles of LiCoO2/Li cell in 1.0 M LiPF6-EC/DEC(1:1 vol%) without additive and with 1.0 wt% FEC at different cut-off voltages.

Y. Park et al. / Journal of Molecular Structure 1069 (2014) 157163

impedance spectrum (EIS) also was measured by PARSTAT 2273,

according to the three-electrode system. The LiCoO2 electrode
was used as the working electrode, and two lithium foils as the
counter and reference electrodes, respectively. The EIS measurements were conducted within a frequency range of 101106 Hz
with an ac voltage signal of 5 mV. An XPS analysis was conducted
using a VG Multilab 2000 spectrometer (ThermoVG Scientic) in
an ultra-high vacuum, which system utilizes an unmonochromatized Mg Ka (1253.6 eV) source and a spherical section analyzer.
The accuracy of the binding energy (BE) values was 0.1 eV. In
the analysis of the XPS peaks, the BEs were corrected for specimen
charging by referencing the C 1s peak to 284.6 eV. The background
was subtracted by Shirleys method, and spectrum deconvolution
was accomplished by Voigt-prole tting. Synchronous and asynchronous 2D correlation spectra were obtained by using the same
software as those described previously [3035].
3. Results and discussion
In the electrochemical performance comparison, galvanostatic
chargedischarge tests were conducted with a LiCoO2/Li cell in
FEC-free and FEC-containing electrolytes, respectively. As shown
in Fig. 1, the irreversible capacity of the LiCoO2/Li cell at 4.2 and
4.5 V, without FEC additive, was 6.4 and 8.7 mA h g1, respectively,
whereas, with 1.0 wt% FEC additive at the same voltages, the
capacity was 4.2 and 5.1 mA h g1, respectively. This irreversible
capacity loss in the FEC-containing electrolyte, which was smaller
than in the FEC-free electrolyte, was correlated with SEI formation
due to decomposition of organic electrolytes in the electrochemical
reaction. This result indicated that the structure of the SEI lm (e.g.

159

composition, thickness, morphology) was altered by the addition

of FEC.
The cyclic voltammograms of the LiCoO2/Li cell for the electrochemical reactions in the FEC-free and FEC-containing electrolytes
are shown in Fig. 2. The proles with and without FEC appeared to
be similar, thus signifying that the lithium reaction mechanism
was not altered by the FEC additive. However, the separation of
the two main peak positions at 4.05 and 3.81 V, as correlated with
delithiation/lithiation, grew larger in the FEC-free electrolyte with
increasing electrochemical cycles. Also in the FEC-free electrolyte,
the magnitude of the currents in the forward and reverse scans
was more reduced than in the FEC-containing electrolyte. This
means that the addition of FEC increased the electron-transfer rate
on the LiCoO2 surface.
To better understand the structure of the SEI lm, we analyzed
the XPS spectra of the LiCoO2 electrode without additive and with
1.0 wt% FEC at different voltages. Fig. 3 plots, specically, the C 1s
XPS spectra. For the LiCoO2 electrode without additive, three peaks
at 291.4, 287.2 and 285.2 eV were observed for the aged electrode,
and were assigned to the CFx from the binder (PVdF), to the C
atoms in an oxygen environment such as CAO, C@O and carbonates produced by the decomposition of the electrolyte, and to the
hydrocarbon in the conductor and/or organic electrolyte, respectively [35]. Upon charging, the intensity of the CFx band was decreased and shifted down from its unperturbed position, while the
other bands, due to CAO, C@O and carbonate-containing SEI components, were increased, as reected SEI formation on the LiCoO2
cathode surface. Another explanation is the decomposition of the
binder during the electrochemical reaction [36]. As for the LiCoO2
electrode with 1.0 wt% FEC additive, there was no noticeable

Fig. 2. Cyclic voltammograms of LiCoO2/Li cell in 1.0 M LiPF6-EC/DEC(1:1 vol%) without additive and with 1.0 wt% FEC for different voltage ranges.

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Y. Park et al. / Journal of Molecular Structure 1069 (2014) 157163

Fig. 3. C 1s XPS spectra of LiCoO2 particles (a) without additive and (b) with 1.0 wt% FEC during overcharge process.

difference between its C 1s spectral features and those of the

LiCoO2 electrode without FEC.
Fig. 4 plots the F 1s XPS spectra of the LiCoO2 electrode without
and with 1.0 wt% FEC. Two bands at around 687.5 and 685.1 eV,
which were assigned to PVdF and/or Li salt and LiF, respectively
[18,36,37], appeared for both electrodes. Upon charging, the intensity of LiF increased for both samples, though the magnitude was
more pronounced for the electrode with 1.0 wt% FEC. LiF usually
is generated via the decomposition of LiPF6 [38]:

LiPF6 ! LiF PF5 :

This indicates that the LiF SEI component is formed on the LiCoO2
surface as a result of the decomposition of Li salt during the charging process. In this light, the present XPS results suggest that the
surface components of the LiCoO2 electrode are noticeably changed
during the chargedischarge process and that the SEI-component
ratio is affected by FEC addition.
To better understand the mechanism of the electrochemical
reaction at the electrode/electrolyte interface, we applied 2D correlation analysis to the obtained C 1s XPS spectra. Fig. 5(a) and (b) plot,
respectively, the synchronous and asynchronous 2D correlation C 1s
XPS spectra of the charged LiCoO2 electrode in FEC-free electrolyte.
The power spectrum extracted along the diagonal line in the synchronous 2D correlation spectrum is also shown at the top of
Fig. 5(a). As shown in Fig. 5(a), ve peaks at 291.7, 289.9, 287.9,
286.4, and 284.5 eV appeared, which could be assigned to the
CFx, to C atoms in the three-oxygen environment such as Li2CO3

and ROCO2Li, to C atoms in the two-oxygen environment such as

oxalate, to C atoms in the one-oxygen environment such as polyethylene oxide PEO (ACH2ACH2AOA)n and ROLi, and to the CAC/CAH
bond, respectively [18]. The cross-peak at 291.7 eV was negatively
correlated with the others, indicating that SEI components were
formed on the cathode surface. By comparing the cross-peak signs
between the synchronous and asynchronous 2D correlation spectra,
the sequence of the spectral intensity changes with increasing voltage was determined as follows: 292.1 (due to CFx) ? 290.4 (due to
C atoms in three-oxygen environment) ? 286.4 (due to C atoms in
one-oxygen environment) ? 288.1 (due to C atoms in two-oxygen
environment) ? 284.6 (due to CAC/CAH) eV.
Fig. 6 plots, respectively, the synchronous and asynchronous 2D
correlation C 1s XPS spectra of the charged LiCoO2 electrode in FECcontaining electrolyte. The power spectrum extracted along the
diagonal line in the synchronous 2D correlation spectrum is also
shown at the top of Fig. 6(a). From the synchronous correlation,
we obtained the four peaks at 292.1, 290.6, 286.4, and 284.6 eV,
which could be assigned to the CFx, polycarbonate, CAO polymerized carbonate, and CAC/CAH bond, respectively. The intensity
ratio of the power spectrum suggests that polycarbonate becomes
the dominant species in the SEI lm of FEC-containing electrolyte.
Analysis of the 2D-correlation spectra showed the following
sequence of spectral events with increasing voltage: 291.6 (due
to CFx) ? 284.7 (due to CAC/CAH) ? 290.6 (due to C atoms in
three-oxygen environment) ? 287.4 (due to C atoms in one-oxygen environment) eV. The analytical results suggest that, initially,

Fig. 4. F 1s XPS spectra of LiCoO2 particles (a) without additive and (b) with 1.0 wt% FEC during overcharge process.

161

286.4

284.5

289.9

291.7

287.9

Y. Park et al. / Journal of Molecular Structure 1069 (2014) 157163

(a)

(b)
Binding Energy (eV)

Binding Energy (eV)

284

286

288

290

284

286

288

290

292

292

294

294
294

292

290

288

286

294

284

290

292

288

286

284

Binding Energy (eV)

Binding Energy (eV)

Fig. 5. (a) Synchronous and (b) asynchronous 2D correlation C 1s XPS spectra of LiCoO2 particles in FEC-free electrolytes during overcharge process. The solid and dotted lines
represent positive and negative cross-peaks, respectively.

electrolytes, battery performance is enhanced. In order to conrm

this hypothesis, we obtained, for different charging voltages, the
impedance data on the LiCoO2 cathode without and with 1.0 wt%
FEC. Fig. 7 shows Nyquist plots for the LiCoO2 electrodes obtained
at different potentials during the rst cycle. Each plot consists of a
depressed semicircle and a distorted Warburg tail or a capacitive
loop. At higher frequencies, the depressed semicircle can be attributed to the formation of passive lm, whereas in the lower frequency range, this feature is due to the charge transfer. The
Warburg tail was attributed to solid-state diffusion of lithium ions

28
84.6

29
92.1
1

286..4
2

2 6
290.6

the PVdF binder and electrolyte components are decomposed, after

which, SEI components such as polycarbonate, polyethylene oxide
PEO and ROLi are formed on the LiCoO2 cathode surface. In FECcontaining electrolyte, the polycarbonate components are more
abundant than in FEC-free electrolyte.
Polycarbonate-based polymers have been successfully used as
Li+-conducting materials in Li-ion batteries. The present 2D correlation results imply, then, that the formed carbonates in SEI lm
can act as Li+-conducting materials that can reduce the electrode/
electrolyte interfacial impedance. Consequently, in FEC-containing

(b)
284

284

286

286

Bind
B
ding
g Ene
E ergyy (e
eV))

Bind
B
ding
g Ene
E ergyy (e
eV))

(a)

288

290

288

290

292

292

294

294
294

292

290

288

(eV))
d g Energy
e gy (e
Binding

286

284

294

292

290

288

286

284

Binding
(eV))
d g Energy
e gy (e

Fig. 6. (a) Synchronous and (b) asynchronous 2D correlation C 1s XPS spectra of LiCoO2 particles in FEC-containing electrolytes during overcharge process. The solid and
dotted lines represent positive and negative cross-peaks, respectively.

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Y. Park et al. / Journal of Molecular Structure 1069 (2014) 157163

Fig. 7. Nyquist plots of LiCoO2/Li cell in 1.0 M LiPF6-EC/DEC(1:1 vol%) without and
with 1.0 wt% FEC additive.

into the bulk metal oxide. The resistance values of the LiCoO2
electrode without FEC additive were twice as high as those of the
electrodes with FEC additive. These results indicate that FEC
additive forms, on the surface of LiCoO2, an SEI layer that effects
a lower electrode/electrolyte interfacial impedance, thereby
improving the electrochemical performance.
4. Conclusions
The electrochemical performance of the LiCoO2/Li cell in
FEC-free and FEC-containing electrolytes was investigated by XPS
and 2D correlation spectroscopy. The electrochemical results showed
that FEC reduces the irreversible capacity loss incurred in the
chargedischarge process. Based on an analysis of the 2D correlation XPS spectra, we suggest an SEI-formation mechanism according to which the PVdF binder and electrolyte components are
decomposed, followed by formation of SEI components on the
LiCoO2 cathode surface. It was found, as corroborated by the results
of an EIS analysis, that the addition of FEC increases the polycarbonate content in the SEI layer, which enhances the ion conductivity of SEI lm and improves, through the lowered interfacial
impedance thereby, electrochemical performance.
Acknowledgment
This work was supported by National Research Foundation of
Korea (NRF) grants funded by the Korea government (MEST) (No.
2009-0087013).
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