Research Article

Received: 23 February 2010 Accepted: 25 January 2011 Published online in Wiley Online Library: 1 April 2011

(wileyonlinelibrary.com) DOI 10.1002/jrs.2930

A novel combinative Raman and SEM mapping

method for the detection of exfoliation
of graphite in electrodes at very positive
potentials
Andreas Hintennach† and Petr Novák∗
The random exfoliation at very positive potentials (>5 V vs Li/Li+ ) of graphite (used as a conductive component in positive
electrodes of lithium-ion batteries) was investigated with in situ Raman microscopy and post mortem scanning electron
microscopy (SEM). A novel semiautomated computational method for the data analysis of both characterization methods was
developed to correlate Raman and SEM information with good lateral resolution, in order to locate exfoliated graphite particles.
Proof is given that the exfoliating particles detected via the semiautomatic in situ Raman microscopy mappings correctly
describes exfoliated areas, as confirmed via post mortem SEM pictures. Copyright
c 2011 John Wiley & Sons, Ltd.
Supporting information may be found in the online version of this article.

Keywords: SEM; Raman microscopy; lithium-ion battery; positive electrodes; exfoliation

Introduction mapping methods provide an overview of a selected area of the

graphite electrode (typically about 100 µm × 100 µm), providing
Electrochemical energy storage[1 – 4] is one of the key technologies
information, e.g. about the homogeneity of intercalated lithium
in a clean energy economy. The need for the reduction of carbon
into the graphene layers. There have been many reports on in situ
dioxide emission together with the increase in crude oil prices has
Raman spectroscopy with both time and space resolution focused
led to the exigency of augmentation of the energy efficiency of
on lithium-ion batteries and, frequently, on graphite electrodes
technical devices, e.g. cars. The current technology of choice for
and single graphite particles. However, in general the published
the near future is hybrid electric vehicles.[5,6] With the need for
results are focused on the negative graphite electrodes[15,29,38 – 43]
increase in the percentage of electric power (and a downsized
and/or on the use of graphite as conductive additive for standard
combustion engine) in mind, rechargeable lithium-ion batteries
‘4 V’ positive electrodes containing other active materials than
are considered to be the best energy storage devices. Compared
graphite.[44 – 49]
to nickel–metal hydride batteries, lithium-ion batteries can store
On the other hand, graphite is also used as an additive in the
about 2–3 times more energy per unit mass (energy density).[1 – 3]
positive electrodes of lithium-ion batteries, normally to increase
Besides the energy density, the long-term stability (high cycling
the electronic conductivity of the electrode mass. Of current
stability and long calendar life) of the batteries is a key factor for
interest is the behavior of graphite as the conductive additive in
their use in cars.
the ‘5 V’ future positive electrodes. Such electrodes offer a higher
Graphitic carbon is a key component of lithium-ion batteries. On
energy density because of the higher voltage. But they work in a
one hand, because of its high reversible specific charge of 372 Ah
potential region where (1) the intercalation of anions into graphite
kg−1 , high electronic conductivity, and good cycling stability,
is possible (as known from the so called ‘dual graphite’ cells – e.g.
graphitic materials are widely used in the negative electrodes of
the publication of Seel and Dahn[39] where the electrochemical
lithium-ion batteries.[7 – 10] For graphite serving as the negative
and structural aspects of anion intercalation into graphite are
working electrode, degradation effects due to exfoliation of the
discussed) and (2) as a possible deterioration mechanism the
graphene layers have been reported, with the consequence of
exfoliation of graphite can occur.[50] In this paper, we focus on
a deterioration of the cycling stability.[11 – 13] Several mechanisms
the detection of the exfoliation of graphite particles cycled under
have been proposed to explain the exfoliation as a consequence
of graphite surface characteristics,[14 – 17] the amount of defects at
the graphite surface,[18] and the surface chemistry.[15] To describe
∗ Correspondence to: Petr Novák, Paul Scherrer Institut, Electrochemistry
the amount of defects, earlier works have demonstrated that the
Laboratory, CH-5232 Villigen PSI, Switzerland. E-mail: petr.novak@psi.ch
active surface area of graphite[19,20] plays an important role in its
tendency for exfoliation. † Current address: Department of Mechanical Engineering, Electrochemical
Raman microscopy has proved to be a method of choice Energy Laboratory, Massachusetts Institute of Technology, 77 Massachusetts
for the in situ characterization of surfaces of working graphite Avenue, Building 31, Room 146, Cambridge, MA 02139, USA.
electrodes.[13,20 – 29] For this, in situ and post mortem surface
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Paul Scherrer Institut, Electrochemistry Laboratory, CH-5232 Villigen PSI,

mapping techniques have been developed.[22,28 – 37] These Raman Switzerland

J. Raman Spectrosc. 2011, 42, 1754–1760 Copyright

c 2011 John Wiley & Sons, Ltd.
Raman and SEM mapping method
such rather abuse conditions at very positive potentials (>5 V
vs Li/Li+ ). The effect of electrochemical cycling is analyzed with
quantitative and qualitative methods of in situ and post mortem
Raman mapping and is correlated with post mortem scanning
electron microscopy (SEM) results. The novel technique described
below helps to detect and understand the degradation effects
in lithium-ion batteries when they are related to the exfoliation
of the graphitic conductive additive. Clearly, this deterioration
mechanism is of very high practical importance for electrode
developers.
Finally, we wish to stress that our scientific focus was on the
development of the method as described below. To this point,
the Raman spectral characteristics were used as a tool to identify
the spots where the exfoliation occurred. Fundamental questions
related to the evolution of Raman spectra were out of the focus of
this work.
Experimental
Electrode and in situ cell preparation
A standard graphite (90 wt.%, TIMREX SFG44, TIMCAL SA, Bodio,
Switzerland) was used as a model material to investigate its
possible deterioration when used as an electrically conductive
additive in the positive electrodes of lithium-ion batteries. The
SFG44 sample was selected among many available graphites as an
optimal model material, based on both our own X-ray diffraction
(XRD)[50] data and also the spectroscopic work investigating the
influence of different graphite types on the exfoliation behavior
of graphite at different potentials. No electroactive oxide was
used in such model electrodes. Polyvinylidene fluoride (PVDF,
8 wt.%, SOLEF 1015, Solvay) dissolved in N-methylpyrrolidinone
(NMP, Fluka) was used as a binder, and the surfactant Triton X-
305 (2 wt.%, Sigma-Aldrich) was used to avoid agglomerations
of graphite particles during the preparation of the electrodes.
The ratio of the materials in the model electrodes was 90 : 8 : 2
(graphite/PVDF/surfactant, by mass after drying). To prepare a
suspension, all used materials were mixed with an ultrasonic stirrer
(Hielscher UP200H, Teltow, Germany) for 2 min at 100% amplitude
without pulsing. The suspension was sliced with a doctor-blade on
an aluminum foil and then dried under vacuum at 100 ◦ C overnight
to achieve a final ‘dry’ height of 250 µm of the electrode mass.
Afterwards circular working electrodes with a diameter of 13 mm
were punched out and dried further under vacuum at 120 ◦ C
overnight. Then, in an Ar-filled glove box with less than 1 ppm
of oxygen, nitrogen and water, the in situ Raman cell[17,51 – 53] was
assembled and hermetically sealed. A fiber glass separator (1 mm
thick) soaked with 300 µl of electrolyte [1 M LiClO4 in ethylene
carbonate (EC)/dimethyl carbonate (DMC) 1 : 1] was used. LiClO4
was used because of its less distracting influence on the in situ
Raman signal.[13,51,54] Metallic lithium served as both the reference
and counter electrode. In situ Raman spectra were collected at
25 ◦ C through a 200-µm thick glass window with a confocal
Raman microscope (LabRAM HR, HoribaJobinYvon SA, Bensheim,
Germany), using a He–Ne laser as exciting source (632.8 nm, 18
mW). The laser light was focused through a small hole (d ≈ 1 mm,
punched before coating) in the current collector onto the surface
of the graphite electrode with an 80× objective (Olympus) and
filtered to 0.9 mW (measured with a meter: Coherent FieldMate,
Santa Clara, CA, USA) during measurement and 0.13 mW during
focusing (built-in filter dial), to avoid thermal degradation. The
electrodes were galvanostatically cycled from 2.0 to 5.5 V vs Li/Li+
J. Raman Spectrosc. 2011, 42, 1754–1760 Copyright

c 2011 John Wiley & Sons, Ltd.
using standard electrochemical equipment to study exfoliation
because of repeated excursions to very positive potentials (>5 V vs
Li/Li+ ). The specific charge for the C-rate calculation was assumed
to be 140 Ah kg−1 . The galvanostatic cycling was performed at
C/10 for the first three cycles with subsequent 17 cycles at C/20.
There were no idling periods at the potential reversal points.
Electrode characterization
Raman mappings of the graphite electrode were recorded (both
in situ during the electrochemical cycling and post mortem) using a
10 × 10 matrix with a lateral working distances of 20 µm. For every
point of a Raman map five independent spectra were recorded to
check for possible changes in the local structure of the graphite
electrode because of the thermal impact of the focused laser spot
(filtered to about 0.9 mW).
Figure S1 (Supporting Information) shows two typical SEM
pictures of the surface of an exfoliated graphite electrode. As
standard SEM pictures do not offer the possibility to draw
a correlation between them and in situ Raman microscopy
results – with respect to the localization of exfoliated areas on
the same surface (and the same spot) of the electrode – a unique
marker had to be found on the surface of the electrode. Laser
marking turned out to be a convenient option. Thus the same
optics could be used for the laser marking process and the
Raman characterization. To create these markers at the surface of
the electrode in a reproducible way, three points were focused
outside of the area of the Raman mapping below line no. 10 (in the
negative y direction and at positions 1, 2, and 7, in the x direction;
Fig. 1). Normally, for about 4 min a laser power of about 4.5 mW
was applied. The thermal impact on the surface of the electrode
with the concentrated spot of laser radiation burned visible marker
spots (holes) on the surface with known coordinates. Figure S2
shows a representative SEM picture of such a burned hole. These
three thermally created holes could be addressed again in the post
mortem recorded pictures from the SEM. Thus, the same area of the
surface of the electrode was characterized by Raman microscopy
and SEM. Note that the coordinates of all surface features are
known because of the fact that the same objective of the Raman
microscope is used for characterization and marking and therefore
the in situ Raman measurements and the markings have the same
coordinate system.
After the in situ Raman mapping using the 10 × 10 matrix was
completed, six additional points were chosen on two different
graphite particles (distance approximately 300 µm, three points
on each particle) to acquire independent information from two
defined particles and to verify the results of the 10 × 10 in situ
Raman mapping.
After dismounting the electrodes of the in situ Raman cell,
the electrodes were washed with pure EC/DMC 1 : 1 and then
vacuum-dried. SEM images were then recorded using either a
Zeiss LEO440, SE1 detector, 3 kV, or Zeiss Ultra, SE2 or InLens
detector, 3 kV, to obtain a post mortem overview of the surface of
the working electrode. As the laser-burned markers on the surface
of the electrode were visible, the local coordinates of every single
SEM image could be attached to the data files describing the SEM
images. For larger areas, an SEM mapping was performed. With the
coordinate information and the computer software ImageJ JAVA,
all surface images could be evaluated and correlated with the
Raman spectral information (using Cobol85 script, function-based
communication with Raman software). An additional software
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package was written (Cobol85 script, file-based communication
wileyonlinelibrary.com/journal/jrs

Figure 1. Schematic representation of the arrangement of the in situ
Raman mapping technique. The measurement points within the shown
grid (an exemplary width of 10 × 10 points was chosen) are regular
measurement points, whereas the three additional points are laser-burned
markers on the surface of the electrode.
port) to allow the automated evaluation of the spectra data sets
with respect to band shifts and the ratio of the integrals of
the D, G, and E bands (see Section on Results). A subsequent
correlation of the SEM pictures with this Raman information
permitted automated colorization of the electrode SEM pictures
with respect to, e.g. the exfoliated areas. Different γ values (relation
of the proportion of black to white color) of the monochromic
information set in the second layer of the picture were used. A
following analysis of the false color information of the image was
performed with standard image evaluation routines (ImageJ JAVA)
to evaluate the ratio of exfoliated areas to non-exfoliated areas.
Afterwards, an automated statistical analysis of the surface of the
electrode was executed (S+ , Tibco Software Inc.). To avoid double
counting of exfoliated areas, the distance of every single exfoliated
area at the surface of the electrode to all surrounding exfoliated
areas of the same electrode is included in a file describing the
surface of the electrode with unique data sets. The size of the
total area of exfoliated parts of the electrode is determined by
the number of pixels of the detector of the SEM detecting an
exfoliated area (cf Fig. S3).
Results and Discussion
Highly exfoliated particles of graphite show a typical accordion-
like morphology (Fig. S1). The Raman spectrum of the exfoliated
graphite shows a typical band called the E band (‘exfoliation
band’, Fig. 2). The wavenumber of the spectral signature of the
E band is different from that of the G band of intact graphite
with intercalated ions. This is due to the different environments
of the respective graphene layers – the presence of solvated ions
adjacent to the surface of the exfoliated particles is the obvious
reason.
When the G band starts to broaden with increasing electrode
potential and two side bands begin to grow and become distinct
bands, these additional peaks can be assigned to the intensities of
the interior E2g2 (i) (left part) and bounding E2g2 (b) (right part)
bands of the exfoliated graphite.[13] Owing to changed C–C
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bond force constants because of the exfoliation, the shift of the
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c 2011 John Wiley & Sons, Ltd.
A. Hintennach and P. Novák
Figure 2. Exemplary post mortem Raman spectra of two arbitrarily selected
points on a SFG44 graphite electrode. The electrode was electrochemically
cycled up to very positive potentials (2.0–5.5 V vs Li/Li+ , 20 cycles, 1 M
LiClO4 in EC/DMC 1 : 1). (a) The E band (exfoliation band) detected at the
exfoliated parts of the graphite electrode and (b) the G band (with the
weak shoulder of the D band) seen at the intact parts of the electrode.
E2g2 (b) could be observed.[4,55 – 60] If the graphite were intact, the
typical G and D bands would be seen in the same wavenumber
region [spectrum (b) of Fig. 2],[13,61] and in an in situ experiment
the Raman spectrum development follows the pattern known for
anion intercalation.
The respective bands around 1600 cm−1 can be used as a
spectral fingerprint for the semiautomatic search for exfoliated
areas of the electrode. Figure 3 shows a typical post mortem SEM
image with two representative in situ Raman spectra from different
locations. Using the above-described coordinate information,
changes in the ratio of the intensities of D , G, and E bands
of the local Raman spectra of the graphite electrodes can be
evaluated and correlated with the surface morphology: at the
exfoliated areas on the surface of the graphite electrode, the
Raman spectrum features E bands instead of the G band.
The change with potential in the magnitudes of the integrals
of both parts of this E band is significantly different from the
change in the magnitude of the integrals of the fitted D and G
bands (Fig. 4). Note that the above statement is valid only after the
graphite electrode was partially exfoliated by potential excursions
up to 5.5 V.
The assignment of the overlapping D and E bands of the
Raman spectrum can be performed as follows: As the shoulder
of the G band (the D band) decreases in intensity with a
progressing intercalation of anions into the graphite, the E-band
feature remains visible as a result of the irreversible structural
changes caused by the exfoliation. The irreversible exfoliation
of the graphite material can be indeed detected post mortem
spectroscopically after complete electrochemical cycling. It was
shown in an earlier work[13] for very reductive potentials (i.e. the
intercalation of lithium and the reductive exfoliation of graphite)
that the D and E bands of the Raman spectra of graphite electrodes
can be clearly distinguished by using the additional information
of the ratio of the magnitude of the D and D bands. As the
same behavior was observed for the anion intercalation at very
positive potentials, the assignment was performed here in an
analogous way.
J. Raman Spectrosc. 2011, 42, 1754–1760
Raman and SEM mapping method
Figure 3. Exemplary representation of two selected measurement points
for the combination of the in situ Raman mapping technique with a
post mortem recorded SEM image (Zeiss LEO440, 2 kV, SE1 detector). The
appropriate G- and E-band region is shown in the assigned Raman spectra
for the exfoliated and the non-exfoliated areas on the surface of the
electrode. Electrochemical cycling was performed between 2.0 and 5.5 V
(vs Li/Li+ , 1 M LiClO4 in EC/DMC 1 : 1).
Figure 4. Typical changes with potential of the in situ Raman spectrum of
a graphite electrode during electrochemical cycling up to very positive
potentials (2.0–5.5 V vs Li/Li+ , 1 M LiClO4 in EC/DMC 1 : 1) after ten cycles.
The relation of the integrals of the G and E bands is used to identify the
exfoliation process.
Interestingly, in the in situ Raman spectrum of graphite
electrodes, a significant and reversible shift of the D band with
the potential could be observed in areas where the E band
was detected, i.e. where exfoliation occurred (Figs 5 and 6). The
magnitude of the D-band shift in areas without exfoliation was
less than half that in areas with detected exfoliation. The D band
shifts between 1322 and 1346 cm−1 for increasing potentials
between 3.0 and 5.5 V, with the most significant shift around
4.8 V (vs Li/Li+ ). Obviously, the intensity of the Raman D band
increases with an increasing degree of exfoliation. This is not
surprising because the origin of the D band lies in defects
in the graphite structure and in prismatic surfaces. It is clear
that exfoliation increases the number of defects and, thus, the
J. Raman Spectrosc. 2011, 42, 1754–1760 Copyright

c 2011 John Wiley & Sons, Ltd.
Figure 5. Shift with the potential of the D band of the in situ Raman signal
of a graphite electrode (2.0–5.5 V vs Li/Li+ , 1 M LiClO4 in EC : DMC 1 : 1)
after ten cycles.
Figure 6. Shift with the potential of the D band of the in situ Raman signal
of a graphite electrode after ten cycles. Electrolyte 1 M LiClO4 in EC/DMC
1 : 1. An exemplary standard deviation is shown for the potential of 4.8 V
(vs Li/Li+ ).
surface disorder increases. Consequently, the D band is more
intense. As the shift with potential of the D band is reversible
(Fig. 6), it can be used in addition to the ratio of the integrals
of the E and G bands to define a new marker, which will
help in localizing the exfoliation process of graphite. Therefore,
the semiautomated localization of the areas of the electrode
where exfoliation occurred is facilitated straightforwardly using
the described full set of spectral information (shift of the D
band, ratio of the integrals of D and G bands, ratio of the
integrals of G and E bands, and the post mortem detection of
the E band after electrochemical cycling). In short, intact areas
of the graphite electrode intercalate and de-intercalate anions
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and therefore behave reversibly during cycling and consequently
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 A. Hintennach and P. Novák

Figure 7. (a) Two typical mappings from in situ Raman experiments (10 × 10 mapping points, 250 µm × 250 µm) of a SFG44 graphite electrode during
electrochemical cycling (2.0–5.5 V vs Li/Li+ , 1 M LiClO4 in EC/DMC 1 : 1). Light gray colors indicate non-exfoliated areas, whereas gray and dark gray colors
indicate exfoliated areas. (b) Distribution of the number of exfoliated areas and the total sum of these areas.

show low fluctuation of the spectral data, whereas the exfoliated
(deteriorated) areas show high fluctuation of the spectral data
during cycling.
The post mortem SEM images were evaluated as follows: The
points on the electrode surface correspond to the pixels of the
digital image. The pixels were treated as a grid, as schematically
shown in Fig. S3. Each square represents a pixel of the false color
images to be generated after processing the SEM pictures and
the in situ Raman data. However, as the ability to find exfoliated
areas on the surface of the electrodes is limited by the effective
range of the standard deviation calculated from all the involved
parameters, the total resolution of the SEM images was reduced
accordingly by interconnecting defined pixel areas (grid cell:
in the example of Fig. S3, 2 × 2 pixels were interconnected,
represented in the scheme by the gray area in the middle of the
total square).
Figure S4 shows schematically how the exfoliated particles were
classified. The electrode area is described by the respective Raman
spectra. An automated analysis was performed with respect to
the fluctuations in the set of spectral parameters for D-band
positions and G/E band ratio of intensities and maxima positions.
An increasing deviation from a calculated average was assumed to
indicate exfoliated parts on the surface of the electrode. To every
found exfoliated area (‘considered particle’) in Fig. S4, the area and
the angles of all surrounding other exfoliated areas were assigned,
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small areas forming together a larger area, a minimum angle can
be defined. This is symbolized in Fig. S4 by α ij .
Automated Raman mapping techniques created the maps
shown in the top row of Fig. 7. Different colors indicate exfoliated
and non-exfoliated parts with a given lateral resolution. After a
statistical evaluation of the number and size of exfoliated and non-
exfoliated areas on the surface of the electrode, a quantification
could be drawn as shown in the bottom row of Fig. 7. This
analysis revealed that exfoliation leading to the degradation of
the electrode occurred irregularly on some spots of the electrode
when exposed to highly positive potentials (>5 V vs Li/Li+ ). Indeed,
the exfoliation was confirmed by the examination of the respective
areas of the SEM pictures. Moreover, the assignment of the E band
of the in situ Raman spectrum was confirmed by the quantitative
and qualitative analysis of the post mortem SEM images. Figure 8
shows a typical result confirming the quality of the correlation of
the Raman and SEM result.
Figure S5 shows that the proper selection of the grid size is
essential. The automated recognition of exfoliated particles by
the described statistical analysis is influenced by the defined grid
cell size used for the data analysis. The reason is that the useful
lateral resolution of the Raman spectral information is related
to the surface morphology, especially to the coarseness of the
surface of the electrode. The coarseness of the surface depends
on the degree of the exfoliation of graphite, the type of the used
graphite material, and its particle size distribution. The angle of

resulting thus in a unique address. To avoid multiple counting of incidence of the laser beam is also relevant. If only single pixels

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c 2011 John Wiley & Sons, Ltd. J. Raman Spectrosc. 2011, 42, 1754–1760
Raman and SEM mapping method
(PSI and ETH Zurich) are greatly appreciated. We wish to thank Dr
F. Simmen for her help with the SEM images.
Supporting information
Supporting information may be found in the online version of this
article.
References
Figure 8. Exemplary representation of a post mortem recorded SEM image
(Zeiss LEO440, 2 kV, SE1 detector) with attached false color information
highlighting the exfoliated areas. Electrochemical cycling was performed
between 2.0 and 5.5 V (vs Li/Li+ , 1 M LiClO4 in EC/DMC 1 : 1).
of the final false color images are evaluated to maintain high
resolution, weak peaks might be too weak with respect to the
noise level and therefore not detected. This is why a limit of the
minimum of the grid cell size has to be defined to ensure that
the fluctuation of the signal of the Raman spectra can be evaluated
using statistical means (i.e. without a positive or negative tendency
of the fluctuation of the Raman signal because of the coarseness
of the electrode).
Finally, Fig. S6 shows the typical development of an in situ Raman
spectrum with the cycle number. Typically, the E band (exfoliation
band) evolves with the cycle number and then remains constant
over additional cycles. This can be rationalized by the fact that
every excursion into the very positive potential region increases
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voltage profiles of graphite electrodes cycled up to such very
positive potentials at constant charge and discharge currents,
respectively. The evolution of the voltage profiles with time
corresponds to what is expected and can be compared with
the data published by us and others.[39,50,62] The reader is referred
to our related work for a more detailed discussion.[50,62]
Conclusions
In this work, a novel Raman microscopy-based semiautomatic
method for detection of exfoliated graphite particles in battery
electrodes was developed. In an example, exfoliated areas of
model TIMREX SFG44 graphite electrodes were semiautomatically
detected after repeated excursions to very positive potentials
(>5 V vs Li/Li+ ) with in situ Raman mapping and post mortem
SEM. The results of both techniques were combined using a new
correlating method for the data analysis. Finally, the Raman E
band describing the exfoliation process was detected at exfoliated
graphite particles.
Acknowledgements
Technical assistance of Mr W. Scheifele (PSI) and Mr H. Kaiser (PSI)
is highly appreciated. Scientific discussions with Prof A. Wokaun
J. Raman Spectrosc. 2011, 42, 1754–1760 Copyright

c 2011 John Wiley & Sons, Ltd.
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