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pubs.acs.org/JPCC

Graphene-Based Supercapacitors: A Computer Simulation Study

Youngseon Shim,† YounJoon Jung,*,† and Hyung J. Kim*,‡,§,||
†
Department of Chemistry, Seoul National University, Seoul 151-747, Korea
‡
Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, United States
§
School of Computational Sciences, Korea Institute for Advanced Study, Seoul 130-722, Korea

ABSTRACT: Energy density of supercapacitors based on a single-sheet graphene

electrode is studied via molecular dynamics (MD) computer simulations. Two electrolytes
of different types, pure 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI+BF4
) and
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an 1.1 M solution of EMI+BF4
in acetonitrile, are considered as a prototypical room-

temperature ionic liquid (RTIL) and organic electrolyte, respectively. Structure of ions
near the electrode surface varies significantly with its charge density, especially in pure
RTIL. Specific capacitance normalized to the electrode surface area is found to be higher in
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EMI+BF4
than in acetonitrile solution by 55
60%. This is due to strong screening of the
electrode charge by RTIL ions in the former. The RTIL screening behavior is found to be rather insensitive to temperature T. As a
result, the capacitance of supercapacitors based on pure EMI+BF4
decreases by less than 5% as T increases from 350 to 450 K. The
difference in size and shape between cations and anions and the resulting difference in their local charge distribution as counterions
near the electrified graphene surface yield cathode
anode asymmetry in the electrode potential in RTIL. As a consequence, specific
capacitance of the positively charged electrode is higher than that of the negatively charged electrode by more than 10%. A similar
degree of disparity in electrode capacitance is also found in acetonitrile solution because of its nonvanishing potential at zero charge.
Despite high viscosity and low ion diffusivity of EMI+BF4
, its overall conductivity is comparable to that of the acetonitrile solution
thanks to its large number of charge carriers. The present study thus suggests that as a supercapacitor electrolyte, RTILs are
comparable in power density to organic electrolytes, while the former yield considerably better energy density than the latter at a
given cell voltage.

1. INTRODUCTION in activated carbon. Therefore, electrodes based on graphitic

Electric double layer capacitors (EDLCs), also referred to as
supercapacitors, have emerged as an attractive energy storage
device to complement and even replace batteries in applications
that require rapid energy draw, i.e., high power density.1
5
Commonly used electrode materials for EDLCs are carbon-
based, such as activated carbon, carbon nanofibers, and carbon
nanotubes, because of their commercial availability at relatively
low cost and good properties, such as large surface area, high
capacitance, and long cycle life.4,6 However, the electrochemi-
cally available surface area of these materials during charging is
often limited because charge propagation via ion transport in and
out of small micropores is usually not efficient.4 Thus, in some
cases, small mesopores are incorporated in order to improve
charge transport in microporous materials.4 Low electrical con-
ductivity poses another difficulty in achieving high power density
with activated carbon.
Two-dimensional graphene materials made of atomic carbon
sheets7 provide an exciting alternative to activated carbon for use
in energy-related devices because of their excellent properties,
including large surface area, superior stiffness, high electrical
conductivity, and chemical and thermal inertness.8
10 The large
surface area of graphene, substantially higher than the BET
surface area11 of activated carbon, can lead to a significant
increase in the energy storage capability of supercapacitors. In
addition, since its active surface forms effectively a large flat
structure, ion transport in graphene is much more efficient than
materials hold immense potential to significantly improve both
power and energy densities of energy storage devices, such as
rechargeable lithium ion batteries12 and EDLCs,13
18 and to
increase efficiency of energy conversion in, e.g., solar cells.19,20
In this article, we investigate supercapacitors based on a single-
sheet graphene electrode via MD simulations. While organic
electrolytes are commonly considered for supercapacitors, room-
temperature ionic liquids have also received significant attention,
thanks to their attractive properties, in particular, wide electro-
chemical window, high ion density, nonvolatility, nonflammabil-
ity, and good thermal stability.6,21,22 For instance, RTILs’ large
electrochemical window allows high cell voltage that can lead to a
substantial increase in energy storage capacity of EDLCs, com-
pared to conventional electrolytes.13,23 Recently there have been
several computational efforts to obtain microscopic understand-
ing of supercapacitors using RTILs as an electrolyte.24
32 These
studies have shed light on, e.g., ion structure and distributions
near electrodes of various geometry and their influence on
capacitance. However, we are not aware of any prior analysis of
RTILs vis-
a-vis organic electrolytes in terms of their performance
as supercapacitor electrolytes. In order to gain molecular-level
insight into this important issue with attention focused on
Received: April 13, 2011
Revised: October 12, 2011
Published: October 12, 2011

r 2011 American Chemical Society 23574 dx.doi.org/10.1021/jp203458b | J. Phys. Chem. C 2011, 115, 23574–23583
The Journal of Physical Chemistry C
Figure 1. Model supercapacitor system employed in MD. A single-sheet graphene electrode is interfaced on both sides with an electrolyte (in the
present case, pure EMI+BF4
). For convenience, the supercapacitor system is terminated on either side by introducing another graphene sheet as a
confining wall at a distance 6.43 nm from the central electrode. All graphene sheets, i.e., both the central electrode and confining walls, are rigid, flat, and
parallel to each other.
similarities and differences in their roles in supercapacitors, we
embark on a systematic analysis of pure EMI+BF4
and an
acetonitrile solution of EMI+BF4
as prototypes of these two
liquid classes. In this initial study, we consider only half-cell
properties, i.e., electric potential and capacitance of a single
graphene electrode in an electrolyte. Analysis of full super-
capacitor cells in parallel plate electrode geometry will be
reported elsewhere.33
The outline of this paper is as follows: In section 2, we give a
brief account of the models and methods employed in the
present simulation study. In section 3, we examine the structure
of, and charge distributions resulting from, EMI+ and BF4
ions
(and also acetonitrile molecules in the case of the organic
electrolyte) and their screening behaviors in the presence of a
uniformly charged graphene electrode. A detailed comparison of
the EMI+BF4
and acetonitrile solution cases is made for the
electric potential and capacitance of supercapacitors. For insight
into power density, the electrolyte conductivity is also ana-
lyzed via linear response theory. The influence of temperature on
the energy and power densities of the RTIL-based supercapac-
itor is also considered there. Concluding remarks are offered in
section 4.
2. SIMULATION METHODS
Our model supercapacitor system is composed of a flat, single-
sheet graphene electrode that interfaces with an electrolyte on
either side (Figure 1). In the discharged configuration of the
supercapacitor, the electrode is immersed in either a pure RTIL
consisting of 512 pairs of EMI+ and BF4
or an organic
electrolyte composed of 100 pairs of EMI+ and BF4
and 1024
CH3CN molecules. Hereafter, the former and latter systems will
be simply referred to as the RTIL and organic electrolyte
supercapacitors, respectively. We note that the organic electro-
lyte considered here models a 1.1 M solution of EMI+BF4
with
mole fraction 0.089 in acetonitrile. The combined electrode

electrolyte system was placed between two confining graphene
walls in the xy plane situated at z = (6.43 nm, such that the
electrode surface positioned at z = 0 was parallel to the walls
(Figure 1). Outside of the confining walls was a vacuum. All
graphene sheets, viz., the central electrode and two confining
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walls, were modeled as a rigid and flat layer of 448 sp2-hybridized
carbon atoms with dimensions 3.432  3.398 nm2.
To describe the positively and negatively charged electrodes as
well as the fully discharged case, three different uniform surface
charge densities, σS = ( 0.86e/nm2 and 0, were considered for
the central graphene via partial charge assignments to its C
atoms. The corresponding total surface charges were (10e for
the charged electrode cases. The two confining graphene walls
were electrically neutral regardless of the charge state of the
central electrode. The numbers of RTIL cations and anions were
adjusted to meet the charge neutrality of the entire simulation
system. For instance, in the case of the positive electrode with
10e, we employed 507 cations and 517 anions for pure
EMI+BF4
, while the acetonitrile solution contained 95 cations
and 105 anions. The Lennard-Jones parameters employed for C
atoms of the graphene are ε = 43.2 K and σ = 0.34 nm.34 During
the simulations, the graphenes were held rigid with carbon

carbon bond length lCC = 0.1415 nm.35 For RTIL, the flexible
all-atom description of refs 28 and 36, based on the EMI+ model
in refs 37 and 38 and BF4
in refs 39 and 40, was used. For
CH3CN, we used the fully flexible six-site description of ref 41.
Electronic polarizability42 for both the graphene and electrolytes
was ignored in our present study.43,44
We simulated molecular dynamics of the system in the
canonical ensemble at 350 K using the DL_POLY program.45
The simulation cell was composed of the supercapacitor system
described above, placed in an orthorhombic box of 3.432  3.398
 30.0 nm3. The long-range electrostatic interactions were
computed via the Ewald method, resulting in essentially no
truncation of these interactions. The trajectories were integrated
via the Verlet leapfrog algorithm using a time step of 1 fs.
Simulations were carried out with 10 ns equilibration, followed
by a 10 ns trajectory from which ensemble averages were
computed. To examine the temperature effect on energy storage,
we also studied the RTIL supercapacitor at 450 K. Compared to
the 350 K case, the density of EMI+BF4
was reduced by 5% to
account for thermal expansion.46
3. RESULTS AND DISCUSSION
Structure. We begin with electrolyte structures and their
variations with the electrode surface charge density σS. We
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The Journal of Physical Chemistry C
Figure 2. Average number density of (a) EMI+ and (b) BF4
ions in the
RTIL supercapacitor at 350 K. The corresponding results at 450 K are
shown in (c) and (d). z is the distance from the graphene electrode
measured in nanometers. N represents the fully discharged case with an
electrically neutral electrode, while (+) and (
) denote, respectively, the
positively and negatively charged electrode configurations with the
surface charge density σS = (0.86e/nm2, where e is the elementary
charge. In the inset, the same results for z e 1.5 nm are shown for clear
exposition of nα(z) near the electrode. In (e) and (f), nα(z) around the
electrically neutral and negative electrodes at 350 K is presented,
respectively.
mention at the outset that the electrode surface is fully solvated
(viz., wetted) in the present study, irrespective of T, σS, or elec-
trolytes we employed. For convenience, we employ a Cartesian
coordinate system, where the graphene electrode surface spans
the xy plane (
x0 < x < x0 and
y0 < y < y0) with the origin at its
center and its normal defines the z direction (cf. Figure 1). We
introduce the ion densities averaged over x and y
Z x Z y
n̅ α ðzÞ ¼ A0
1
0 0
dx0 dy0 nα ðx0 , y0 , zÞ
ð1Þ

x0
y0
A0 ¼ 4x0 y0
where A0 is the surface area of the graphene electrode with x0 =
1.716 nm and y0 = 1.699 nm, nα(x,y,z) is the local number density
of solvent species α (α = EMI+, BF4
, or CH3CN) at (x,y,z), and
the center-of-mass of ions and molecules is used to represent the
position of α. The results for the average ion and molecule
densities nα(z) are displayed in Figures 2 and 3. nα(z) for z < 0
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Figure 3. Average number density nα(z) of (a) EMI+, (b) BF4
and (c)
CH3CN in the organic electrolyte supercapacitor using a 1.1 M
acetonitrile solution of EMI+BF4
at 350 K. (d) P(θ) of CH3CN in
the first peak ofR the first solvation layer, i.e., z < 0.4 nm, in (c) with
normalization dθP(θ) = 1. The notation is the same as in Figure 2. In
(d), θ is the angle between the normal to the electrode surface and the
molecular orientation of acetonitrile defined as the C-to-C direction
from its nitrile to methyl groups.
are not shown because it is invariant under z f
z due to
symmetry of our supercapacitor system.
We first consider the results for the RTIL supercapacitor in
Figure 2. Regardless of the electrode charge density σS, electro-
lyte structures show significant fluctuations along z. These
fluctuations, particularly strong in the vicinity of the electrode
surface, extend up to z ≈ 3 nm. Similar spatial fluctuations are
also present near the confining walls at z = (6.43 nm. This
indicates that on average ions form layered structures near flat
surfaces24,27,32,47 and that this ordering persists over a consider-
able distance from the surfaces. Nevertheless, the ion densities
become essentially constant in the region 3.5 nm j z j 4.5 nm,
irrespective of σS. This suggests that RTIL there is nearly bulklike
and thus the presence of confining walls at z = (6.43 nm would
not affect our analysis based on the results obtained for |z| j
4 nm. It is also worthwhile to mention that RTIL distributions
near the central electrode and near the confining walls differ even
when the former is electrically neutral with σS = 0. This is due to
the fact that both sides of the central electrode are exposed to
RTIL, while only one side of the confining walls interfaces with
the electrolyte. Comparison of panels a and b and panels c and d
of Figure 2 reveals that temperature has little influence on RTIL
distributions. Except for a very minor reduction in their structure,
nα(z) of both cations and anions remain essentially unchanged as
T increases from 350 to 450 K.
With this in mind, we consider ion structures in the first
solvation shell (more accurately, solvation layer), which is
defined as the region associated with the local density maximum
located closest to the electrode surface. In the case σS = 0, the first
peak in local densities of the cations and anions result at z = 0.37
and 0.38 nm, respectively (Figure 2a
d). The average ring
orientation of EMI+ in the first solvation shell, i.e., z j 0.45 nm,
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The Journal of Physical Chemistry C
Figure 4. Snapshots of EMI+ and BF4
ions close to (a) electrically
neutral (σS = 0), (b) positively charged (σS = σ(+)), and (c) negatively
charged (σS = σ(
)) graphene electrodes in the RTIL supercapacitor at
350 K. Only the ions with their center-of-mass located within 0.45 nm
from the electrode surface are shown.
is nearly parallel to the graphene surface, forming a π-stacking
structure (cf. Figure 4a below); the average angle between the
normal vector of the electrode surface, i.e., z axis, and that of EMI+
rings there is found to be about 10
.
Also notable is that RTIL structures vary markedly with σS,
especially near the electrode surface. Electrostatic interactions
with the surface charge induce reorganization of ions, which leads
to major structural enhancement and reduction for counterions
and co-ions, respectively, near the charged electrode, compared
to the σS = 0 case. Therefore, around the positive electrode with
σS = 0.86e/nm2(σ(+)) that yields a total surface charge 10e, the
distribution of counterions BF4
exhibits a strong first solvation
shell peak at z = 0.37 nm. By contrast, near the negatively charged
electrode with σS =
0.86e/nm2(σ(
)) and a total surface
charge
10e, BF4
ions, which are now co-ions, are characterized
by the first solvation shell peak that is much lower in height and
located further from the electrode (z = 0.54 nm) than the σS =
σ(+) case. EMI+ ions show essentially the same trend even though
the extent of their peak location variations is considerably less
than that of smaller anions. The first solvation shell peak
positions of the former are z = 0.37 and 0.35 nm for the σ(+)
and σ(
) cases, respectively. Another noticeable feature is that, on
average, counterions and co-ions form alternating layers around
the electrified graphene surfaces (Figure 2f).24,27,32,47 This is
reminiscent of alternating concentric shell structures of counter-
ions and co-ions around a central charge found in bulk RTILs.48,49
For further insight, snapshots of RTIL ions close to the
graphene electrode surface are shown in Figure 4. It clearly
illustrates the population changes of the cations and anions
with σS. It is noteworthy that there is a non-negligible number of
co-ions present close to the electrifed graphene surfaces. We also
mention in passing that in the presence of a neutral electrode,
cations are mainly surrounded by anions and vice versa in their
immediate vicinity.
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Figure 5. Snapshots of ions and solvent molecules close to the electrode
with (a) σS = 0, (b) σS = σ(+), and (c) σS = σ(
) in the organic electrolyte
supercapacitor at 350 K. As in Figure 4, only the ions and molecules with
their center-of-mass located within 0.45 nm of the electrode surface are
shown here.
We turn to the organic electrolyte supercapacitor case in
Figure 3. One of the most salient features is that for the neutral
electrode the first solvation shells of ions are formed consider-
ably further from the electrode than that of acetonitrile. As a
consequence, there are virtually no ions present with their center-
of-mass located within 0.5 nm of the neutral graphene surface,
whereas acetonitrile distribution exhibits a main peak at about z =
0.36 nm. This is well illustrated by the snapshot in Figure 5a. Even
when the graphene is charged with a significant surface charge
density σ((), only a very small number of counterions are present
in the close neighborhood of the electrode, compared to CH3CN
molecules there (Figure 5b,c). Thus the “covering” (i.e., wetting)
of flat graphene electrode surface is effected primarily via acetoni-
trile molecules irrespective of σS, at least in the charge density
range we studied. This is attributed to the low ionic concentration
of the electrolyte solution, which is 1.1 M in the present case, as
well as to the highly dipolar character of acetonitrile. We note that
the ionic concentration in this range is typically used in real
supercapacitors.
In Figure 3d, we have analyzed the orientation of acetonitrile,
in particular, its probability distribution P(θ), where θ is the
angle between the z axis and the orientation of the C
C bond of
CH3CN in the direction from the nitrile to methyl groups. We
considered only the acetonitrile molecules with their center-of-
mass located in the region z < 0.4 nm, corresponding to the first
peak of the first solvation shell in Figure 3c. The average θ value is
θ ≈ 70
in the presence of the neutral electrode, indicating that
the nitrile C of acetonitrile is closer to the graphene surface than
its methyl C. Thus on average, the C
C axis of CH3CN in the
z < 0.4 nm region is slightly tilted from the orientation parallel to
the electrode surface, probably due to steric hindrance arising
from its methyl group. As expected, the tilted orientation is
favored even more near the positively charged electrode because
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The Journal of Physical Chemistry C
Figure 6. Average local charge density Fα(z) (units: e/nm3) of (a)
EMI+ and (b) BF4
in the RTIL supercapacitor at 350 K. In (c), the total
charge density, F+(z) + F
(z), is shown.
of Coulomb attraction between the electrode and the nitrile
group of CH3CN; the resulting average value for θ is about 60
.
In the case of the negatively charged electrode with σ(
),
however, Coulomb repulsion between the two pushes out the
nitrile group, resulting in the average orientation of acetonitrile
parallel to the electrode surface in the first peak of the first
solvation layer. This orientation change is accompanied by a
significant reduction in the first peak height.
Electric Potential. We proceed to the electric potential of the
supercapacitors. For convenience, we decompose the total
electric potential Φ into two components, Φσ and ΦIL, arising
from the graphene surface charge and RTIL ions, respectively. In
the case of the organic electrolyte supercapacitor, there is an
additional contribution ΦCH3CN from acetonitrile. We calculated
ΦIL(z) by integrating the Poisson equation24,26
Z z
ΦIL ðzÞ ¼
4π ∑
α¼( 0
ðz
z0 ÞF α ðz0 Þ dz0 ð2Þ
Z x Z y
Fα ðzÞ ¼ A0
1 dx0 dy0 Fα ðx0 , y0 , zÞ
0 0

x0
y0
where Fα(x,y,z) is the local charge density arising from the
atomic charge distribution of ionic species α, F α(z) is its average
at z, and α = ( denotes sum over ionic species. ΦCH3CN was
obtained in a similar way.
The results for Fα(z) of the RTIL supercapacitor at 350 K are
exhibited in Figure 6. The corresponding results for 450 K are
nearly the same as 350 K (cf. Figure 2a
d) and thus are not
shown there. Both cation and anion charge densities are char-
acterized by strong oscillations in z near the electrode surface.
Surprisingly, the oscillations of the anion charge density are
accompanied by sign changes, especially in the presence of a
positively charged or neutral electrode. This is attributed to the
extended nature of ion charge distributions.28 Specifically, de-
spite its overall negative charge, the B and F sites of BF4
ions
have, respectively, partial positive (+1.1504e) and negative
(
0.5376e) charges and thus play antagonistic roles in their
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Figure 7. Average local charge density Fα(z) (units: e/nm3) of (a)
EMI+, (b) BF4
, and (c) CH3CN in the organic electrolyte super-
capacitor at 350 K. The total charge density, F+(z) + F
(z) + FCH3CN(z),
is displayed in (d).
Figure 8. ΦIL(z) (solid line) and
Φσ(z) (dotted line) in (a) pure
EMI+BF4
and (b) the acetonitrile solution at 350 K. In (b), the
contribution to Φ from acetonitrile, ΦCH3CN(z), is shown in a dashed-
dotted line. For easy comparison of different components, the results for

Φσ(z) rather than Φσ(z) are exhibited, so that it has the same sign as
ΦIL(z). Units for electric potential: V.
contributions to local charge density. While the degree of charge
separation is not as pronounced as BF4
, the charge distribution
of EMI+ has a similar extended character. Comparison with
Figure 2 discloses that for z j 1 nm, charge densities of
electrolytes show much more rapid oscillations with z than their
number densities. By contrast, the oscillatory behavior of the
former nearly disappears for z J 1 nm, while structural order
persists well beyond z = 1 nm. The finite character of atomic
charge distributions of ions is also responsible for this interesting
difference between the electrolyte charge and number densities.
We note that the relaxation of charge oscillations over ∼1 nm
observed here is in reasonable accord with the long-range
charge screening length, 0.5
1 nm, obtained for dipolar solva-
tion in other EMI+-based RTIL systems in different model
descriptions.48,49
Several interesting aspects of Figure 6, in particular, rapid
oscillations for z j 1 nm and flattening for z J 1 nm, are shared
by the corresponding cation and anion charge densities in the
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The Journal of Physical Chemistry C
Figure 9. Profile of total electric potential Φ(z) (in units of V) in the
supercapacitor. Electrolytes employed are (a) pure EMI+BF4
at 350 K,
(b) pure EMI+BF4
at 450 K, and (c) 1.1 M acetonitrile solution of
EMI+BF4
at 350 K. For clarity, Φ(z) at the electrode is set at 0 V for
all cases. For comparison, MD results for Φ(z) for a conventional
capacitor with pure acetonitrile used as a dielectric material at 350 K
are displayed in (d).
acetonitrile solution in Figure 7. The charge density arising from
CH3CN in Figure 7c shows a similar oscillatory behavior. One
important difference is that while F+(z) and F
(z) approach a
positive and a negative value as z increases, the acetonitrile charge
density converges to 0. This is fully expected since acetonitrile
molecules are dipolar, i.e., electrically neutral. Because of the low
ionic concentration, spatial fluctuations of the electrolyte charge
density are governed primarily by acetonitrile for z j 0.7 nm.
The results for Φσ(z) and ΦIL(z) are presented in Figure 8,
while those for Φ(z) are in Figure 9. In the RTIL supercapacitor
case, ΦIL(z) tracks
Φσ(z) very closely except for z j 0.3 nm.
Also their magnitudes are vey similar in nearly the entire
electrolyte region. Thus screening of the electrode surface charge
is effected essentially completely via RTIL ions located mainly in
the first solvation shell. The resulting total electric potential Φ(z)
is very small in magnitude and varies little with z outside of the
first solvation shell region (Figure 9a). In other words, the RTIL
supercapacitor behaves like an ideal electric double layer capa-
citor for z J 0.5 nm. As expected from nα(z) in Figure 2, a rise in
T from 350 to 450 K has nearly a negligible effect on Φ(z) in
RTIL (Figure 9b).
For additional insight, we have analyzed the ion numbers and
charges in the electrolyte volume extending from the electrode
surface to a surface at z (cf. eqs 1 and 2)
Z z
Nα ðzÞ ¼ A0 dz0 n̅ α ðz0 Þ ð3Þ
0 magnitude of Φ(z) between the positive and negative electrodes
Z z
QIL ðzÞ ¼ A0 ∑
α¼( 0
dz0 Fα ðz0 Þ
NCH3CN(z) and QCH3CN(z) are defined similarly. The reader is
reminded that the position of the center-of-mass of α is used for
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Figure 10. Number of (a) cations and (b) anions in EMI+BF4
,
contained in the volume spanning from the graphene electrode surface
to z in the RTIL supercapacitor at 350 K. Their difference N+(z)

N
(z) is presented in (c).
nα(z) and Nα(z), whereas their extended atomic charge distribu-
tion is employed for Fα(z) and QIL(z). Panels a and b of Figure 10
show that populations of counterions increase in a stepwise
manner with z, viz., a very abrupt and steep rise near z = 0.35 nm,
followed by a relatively plateau behavior in the 0.4 nm j z j
0.7 nm region and a rapid increase for z J 0.75 nm. This is more
evidence that counterions form a well-defined layered structure
close to the charged electrodes in the RTIL supercapacitor
(cf. Figure 2).
The results for the difference between cation and anion
populations, ΔN(z) = N+(z)
N
(z), in the RTIL supercapacitor
at 350 K are shown in Figure 10c. Pronounced oscillations of
ΔN(z) up to z ≈ 3 nm in the presence of charged electrodes are the
direct consequence of alternating layered structures of counterions
and co-ions mentioned above (cf. Figure 2f). Since the total surface
charge of the graphene is (10e, the full screening occurs when
ΔN(z) = -5, viz., the total charge in the volume spanning from

z to z, including the electrode charge, is 0. The results in
Figure 10c confirm that the complete screening obtains at z ≈
0.35 nm for both the positive and negative electrodes. Interestingly,
counterions continue to accumulate more than co-ions in the RTIL
as z increases beyond 0.35 nm until |ΔN(z)| reaches a maximum
of ∼15 around z = 0.4 nm. Therefore, the total charge in the
volume
0.4 nm < z < 0.4 nm, including the electrode charge,
becomes positive in the case of the negatively charged electrode and
negative in the positively charged electrode case! This is responsible
for |QIL(z)| > 5e for 0.4 j z j0.5 nm in Figure 11a.
Returning to Figure 9a, we notice a significant gap in the
for z J 1 nm. The magnitude of the potential drop ΔΦS(= Φ(z = 0)

Φ(z ≈ 4 nm)) at the electrode with respect to the bulk
electrolyte shows a sizable difference between the two. MD yields
ΔΦ(+) = 1.12 V with σS = σ(+) and ΔΦ(
) =
1.42 V with σ(
) at
350 K, while PZC (potential of zero charge), i.e., the potential drop
for the neutral electrode, is
0.07 V (Table 1). The corresponding
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The Journal of Physical Chemistry C ARTICLE

Figure 11. (a) QIL(z) in the RTIL supercapacitor at 350 K. (b) QIL(z) Figure 12. Nα(z) of (a) EMI+, (b) BF4
and (c) acetonitrile in the
and QCH3CN(z) and (c) their sum in the organic electrolyte super- organic electrolyte supercapacitor. In (d), the corresponding difference
capacitor. In (b), QIL(z) and QCH3CN(z) are plotted in the solid and in Nα(z) between the cations and anions is shown.
dotted lines, respectively.
electrode charges by ions in the organic electrolyte, compared to
the RTIL. The low ionic concentration of the former is directly
Table 1. Electrode Potential ΔΦS and Specific Capacitance cS responsible for the weak screening. It is also noteworthy that
acetonitrile makes an important contribution to Φ for small z.
solvent σS (e/nm2) ΔΦS (V)a cS (μF/cm2)
Through alignment of its dipole moment (cf. Figures 7c,d and
EMI+BF4
at 350 K 0.86 1.12 5.78 11b,c), acetonitrile mainly governs the electrolyte charge density

0.86
1.42 5.09 and thus the shielding in the region z j 0.7 nm as noted above
EMI+BF4
at 450 K 0.86 1.14 5.54 and reduces |ΔΦS| by 2
4 V. It should nonetheless be stressed

0.86
1.48 4.98
that its cumulative charge QCH3CN(z) vanishes as z increases
beyond ∼1 nm because acetonitrile molecules are electrically
CH3CN/EMI+BF4
at 350 K 0.86 2.00 3.62
neutral. This means that the screening of the electrode charge at

0.86
2.00 3.28
large distances is governed by ions as expected from Figure 8b.
a
ΔΦS at PZC is
0.07 and 0.10 V for the RTIL and organic electrolyte According to Figure 12d, full screening occurs close to z = 1 nm
supercapacitors, respectively.
for the organic electrolyte supercapacitor.
Another difference from the RTIL case is that the positive and
values at 450 K are nearly the same, viz., 1.14,
1.48, and
0.10 V, negative electrodes of the organic electrolyte supercapacitor are
respectively. The difference in size and molecular structure characterized by the same |ΔΦS| (=2 V) (Figure 9c) despite their
between the cations and anions is believed to be mainly respon- substantial difference in ion charge density (Figure 7a,b) and
sible for the |ΔΦ(+)|
|ΔΦ(
)| disparity, which is about 0.3 V populations (Figure 12a,b) at small z. Analogous to the RTIL
irrespective of T. Smaller BF4
anions shield the positively charged capacitor, however, ΔΦS of the organic electrolyte supercapa-
electrode more efficiently via their F sites with a partial negative citor does not vanish at PZC. Specifically, ΔΦS = 0.1 V at PZC
charge (
0.5376e) than bulkier EMI+ cations screen the nega- with respective contributions of 0.3 and
0.2 V from ions and
tively charged electrode. This is manifested as a large peak of acetonitrile. By contrast, PZC is 0 in neat acetonitrile, indicating
height
13e in QIL(z) at z ≈ 0.2 nm around the positively charged that the nonvanishing PZC in the organic electrolyte super-
electrode in Figure 11a. By contrast, the corresponding value capacitor is induced by the ions. We ascribe this to a significant
around the negatively charged electrode is QIL(z) = 3.5e. This difference between EMI+ and BF4
in nα(z) (Figure 3a,b) and
enables anions to reduce the electric field at short distances arising Fα(z) (Figure 7a,b) in the acetonitrile solution, arising from their
from the electrode surface charge better than cations. Since ΔΦS is differing size and shape.
given by the integration of the electric field, better reduction of the For completeness, we have also analyzed a conventional
electric field at short distances yields smaller magnitude for ΔΦS. capacitor, consisting of a single-sheet graphene electrode and a
The results for the organic electrolyte supercapacitor in dielectric material modeled as acetonitrile. Its MD result for
Figures 8b and 9c exhibit interesting differences from those for Φ(z) in the presence of a positive electrode charged with σ(+) is
the RTIL supercapacitor. To be specific, while ΦIL(z) tracks shown in Figure 9d. One prominent feature is that Φ(z) shows a

Φσ(z) analogous to the RTIL supercapacitor case, the differ- bimodal character, i.e., a rapid drop near the electrode and a
ence in their magnitude in the organic electrolyte supercapacitor, linear decrease with z in the region z J 0.5 nm. We notice that
which is about 4
6 V for z J 0.5 nm, is much bigger than the the Φ(z) behavior for z j 0.5 nm is very similar, though lesser
RTIL supercapacitor. This exposes the weak screening of the in extent, to that of the organic electrolyte supercapacitor in
23580 dx.doi.org/10.1021/jp203458b |J. Phys. Chem. C 2011, 115, 23574–23583
The Journal of Physical Chemistry C
Figure 9b. This provides additional evidence that acetonitrile
plays a crucial role near the electrode in the organic supercapacitor.
Linear decay in Φ(z) for z J 0.5 nm in the conventional capacitor,
on the other hand, is a manifestation of incomplete screening of
the electrode charge due to the dipolar character of the solvent,
revealing its clear distinction from EDLCs.
Specific Capacitance. We turn to specific capacitance of the
RTIL and organic electrolyte supercapacitors, normalized to the
total electrode surface area exposed to the electrolyte
 
1 ∂qS  ∂σS  σS
c ¼
S
S  ¼ 1=2 S  ≈ ð4Þ
2A0 ∂ΔΦ ∂ΔΦ 2ΔΔΦS
PZC PZC
ΔΔΦS ¼ ΔΦS
ΔΦS ðat PZCÞ
where qS (=σSA0) is the total electrode charge, A0 is the graphene
surface area (eq 1), and cS is evaluated at PZC. The factor 2 in the
denominator of eq 4 arises because both sides of the graphene
electrode interface with the electrolyte (cf. Figure 1).
The results for cS are compiled in Table 1. For the RTIL
supercapacitor, c(+) and c(
) are, respectively, 5.78 and 5.09 μF/
cm2 at 350 K and 5.54 and 4.98 μF/cm2 at 450 K. A few
comments are in order here: First, since the RTIL distribution
(Figure 2a
d) and thus potential drop hardly change with T as
noted several times above, so does the electrode capacitance. For
the present supercapacitor system based on EMI+BF4
, an
increase in temperature by 100 K leads to a reduction of specific
capacitance by only j4%. Second, the aforementioned difference
in solvation of the positively and negatively charged electrodes,
induced by the difference in size and shape of cations and anions,
and resulting discrepancy in the magnitude of their ΔΦS yield
non-negligible cathode-anode asymmetry50,51 in cS. Our finding
that c(+) > c(
) is in good agreement with prior theory50,51 and
MD study,28,27,32 but is at variance with ref 26, where the
opposite result (c(+) < c(
)) was obtained for a similar system
with a lower electrode surface charge density, 0.5125e/nm2.
Third, despite the complete neglect of electronic polarizability
in our model description for both the electrode and electrolytes,
the MD results we obtained for our graphene-based supercapacitors
are comparable to experimental results for closely related systems.
For example, the specific capacitance of a highly oriented pyrolytic
graphite (HOPG) electrode in N,N-diethyl-N-methyl-N-(2-meth-
oxyethyl)ammonium bis(trifluoromethanesulfonyl)imide was found
to be 2.2
5 μF/cm2.15
As in the RTIL supercapacitor case, the organic electrolyte
supercapacitor also exhibits cathode
anode asymmetry in capa-
citance. The simulation results for T = 350 K are c(+) = 3.62 μF/
cm2 and c(
) = 3.28 μF/cm2. The nonvanishing PZC discussed
above is responsible for this asymmetry in the organic electrolyte
supercapacitor. Interestingly, the relative difference in electrode
capacitance is ∼10% for both capacitors. Nevertheless, it should be
noticed that specific capacitance of the organic electrolyte super-
capacitors is smaller than that of the RTIL supercapacitors by
1.8
2.2 μF/cm2. This corresponds to a ∼35% diminution in the
acetonitrile solution, compared to the pure EMI+BF4
case. As
analyzed above, this decrease is attributed primarily to the weak
ionic screening of the electrode charges in the acetonitrile solution.
The result that RTIL supercapacitors exceed organic electro-
lyte supercapacitors in electrode capacitance is one of the major
findings of the present work. This means that in addition to their
wide electrochemical window, RTILs offer another important
23581
ARTICLE
Figure 13. Time correlation function of the ionic current normal to the
electrode surface in (a) RTIL and (b) organic electrolyte supercapaci-
tors at 350 K.
advantage over organic electrolytes in energy density; viz., use of
RTILs would improve the capacitance of the supercapacitors
significantly, compared to organic electrolytes, even at the same
cell potential. Another important finding is that specific capaci-
tance of RTIL supercapacitors is rather insensitive to tempera-
ture, provided that the electrode surface is fully wetted by ions. As
such, RTILs would provide a promising class of electrolytes for
efficient energy storage in a broad temperature range.
Ion Conductivity. To obtain insight into power density of the
RTIL and organic electrolyte supercapacitors, we briefly consider
electrolyte conductivity in the direction perpendicular to the
electrode surface. In the Green
Kubo formulation based on
linear response theory, ion conductivity along the z direction, i.e.,
normal to the electrode surface, is related to the time correlation
function of collective ionic current Jz(t) as
1 Z ∞
σ GK ¼ dt CJJ ðtÞ ð5Þ
VkB T 0
CJJ ðtÞ ¼ ÆJz ð0ÞJz ðtÞæ
N
Jz ðtÞ ¼ ∑ qi vz, i ðtÞ
i¼1
where V is the volume of the system, kB is Boltzmann’s constant,
qi and vz,i are the charge and z-component of center-of-mass
velocity of ith ion and Æ...æ represents an equilibrium ensemble
average. For comparison, we also consider the conductivity
estimated via the Nernst
Einstein equation
∑
1
σ NE ¼ nα q2α DGK, α ð6Þ
kB T α ¼ (
Z ∞
DGK, α ¼ Nα
1 ∑
i∈α 0
dt Ævz, i ð0Þvz, i ðtÞæ
where qα, nα, and Nα are, respectively, the charge, number
density, and total number of ions of species α, i ∈ α means
sum over all ions of species α, and DGK,α is their translational
diffusion coefficient along z. We note that σGK reduces to σNE if
the contribution of cross correlation in CJJ(t) is ignored com-
pletely in eq 5.
The results for CJJ(t) are displayed in Figure 13 and those for
the conductivities and diffusion coefficients are compiled in
Table 2. We first consider the RTIL supercapacitor case.
Figure 13a shows that its CJJ(t) varies little with the electrode
charge density σS. Though not presented there, we mention that
the temporal behaviors of CJJ(t) at 450 K, including the
dx.doi.org/10.1021/jp203458b |J. Phys. Chem. C 2011, 115, 23574–23583
The Journal of Physical Chemistry C
Table 2. Translational Diffusion Coefficient and Ion Conductivity Normal to the Electrode Surfacea
solvent σS (e/nm2) DGK,+
EMI+BF4
0.86 0.20 (0.52)
0.0 0.20 (0.47)

0.86 0.20 (0.47)
CH3CN/EMI+BF4
0.86 1.3
0.0 1.3

0.86 1.3
a
The system temperature is T = 350 K. Results for the RTIL supercapacitor at 450 K are given in parentheses. Diffusion coefficients and conductivities
are measured in units of 10
9 m2 s
1 and S/m, respectively.
frequency and relative amplitude of oscillations, are very close to
those at 350 K. Thus regardless of σS and T we considered, the
ion conductivity along z determined via eq 5 remains largely
unchanged (σGK = 0.26
0.29 S/m). DGK,α, on the other hand,
shows a marked increase with T. This difference in the T
dependence arises primarily from the presence of the T
1 factor
in σGK in eq 5, which is absent in DGK,α. Another noteworthy
aspect is that σNE obtained with the neglect of the cross
correlation in CJJ(t) overestimates the actual conductivity,
viz., σGK, by more than a factor of 2. This reveals an important
role played by the cross correlation in the determination of
conductivity; it cancels a significant part of the contribution
from the self-correlation component of CJJ(t) and thus re-
duces ion conductivity substantially. It is worthwhile to note
that the relaxation behavior of CJJ(t) in Figure 13a is very
similar to that in pure EMI+PF6
studied in ref 52 even though
anionic species are different.
CJJ(t) of the acetonitrile solution in Figure 13b shows an
interesting departure from that of RTIL. Specifically, relaxation
dynamics of the former become decelerated and its librational
character attenuated with increasing t, compared to the latter.
While this kind of relaxation behavior sometimes leads to
“superdiffusion”,53,54 we found that when integrated over t, CJJ(t)
for the present organic electrolyte supercapacitor system yields a
proper plateau behavior and thus well-defined conductivity. As in
the RTIL supercapacitor case, σGK is considerably smaller than
σNE, confirming the importance of the cross-correlation effect.
Comparison of the RTIL and organic electrolyte supercapa-
citor results at 350 K shows a couple of noteworthy features.
First, the ion translational diffusion coefficients along z in
acetonitrile solution are more than 6-fold greater than those in
EMI+BF4
because the latter is considerably more viscous than
the former. Second, the conductivities of the RTIL and organic
electrolyte are comparable. This is due to the high ion density,
i.e., large number of charge carriers, in the former, which com-
pensates for low mobility of its individual charge carriers.
4. CONCLUDING REMARKS
In this article, we have studied supercapacitors based on a
single-sheet graphene electrode via MD. Two different electro-
lytes, i.e., neat EMI+BF4
and a 1.1 M acetonitrile solution of
EMI+BF4
, were considered. One of our key findings is that
specific capacitance of the electrode normalized to its surface area
is 55
60% higher when pure EMI+BF4
is employed as an
electrolyte than the acetonitrile solution. Strong and effective
screening of electrode charges by RTIL ions close to the
electrode is mainly responsible for high capacitance of the RTIL
supercapacitor. Specific capacitance of the positively charged
23582
ARTICLE
DGK,
σNE σGK
0.21 (0.44) 0.59 (1.0) 0.27 (0.29)
0.21 (0.42) 0.59 (0.96) 0.27 (0.28)
0.21 (0.41) 0.59 (0.95) 0.26 (0.27)
1.4 0.73 0.32
1.3 0.72 0.33
1.3 0.72 0.32
electrode was found to be considerably larger than that of the
negatively charged electrode in both EMI+BF4
and acetonitrile
solution. This cathode
anode asymmetry50,51 is ascribed to
differing screening effciency arising from the difference in size
and molecular structure between the cations and anions.
To gain insight into power density, we analyzed ion conduc-
tivity. It was found that ion conductivity in the direction normal
to the electrode surface is larger in the acetonitrile solution than
in pure EMI+BF4
but only by ∼20%. This result suggests that all
other things being equal, the two electrolytes would be largely
comparable in power density.
The effect of temperature on the supercapacitor performance
was also examined. Interestingly and importantly, specific capa-
citance and ion conductivity of the RTIL supercapacitors were
found to vary little with T. This finding, together with the results
summarized above in this section, indicates that RTILs are a
viable candidate to replace conventional electrolytes in energy
storage devices, which has promising potential for a good and
reliable performance in energy storage and delivery over a
significant temperature range. It would thus be very worthwhile
in the future to extend the present study to other supercapacitor
systems composed of differing RTILs and/or electrodes to find
optimal conditions, configurations, and combinations of electro-
lytes and electrode materials for efficient energy storage.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: yjjung@snu.ac.kr; hjkim@cmu.edu.
Present Addresses
)
Carnegie Mellon University.
’ ACKNOWLEDGMENT
This work was supported by the National Research Founda-
tion of Korea (NRF) grants funded by the Korean Government
(MEST) (Nos. 2011-0001212 and 2011-0018038). Y.S. ac-
knowledges the financial support from the BK 21 Program
of Korea.
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23583 dx.doi.org/10.1021/jp203458b |J. Phys. Chem. C 2011, 115, 23574–23583