where, I is the current (in amps) used for charge – discharge cycling, t is the time (in seconds) of

discharge, m is the mass (in grams) of the active material and D E is the operating potential window (in
volts) of charge – discharge. Fig. 1 shows the powder XRD pattern for graphite, GO, graphene and N-
Graphene prepared in di ff erent volumes of ammonium hydroxide. The (002) plane of graphite is clearly
seen at a 2 q of 26.54 (JCPDS # 656212) with interlayer spacing ( d value) of 0.33 nm, while that of GO is
shi ed from 26.54 to 11.07 indicating the increase in ‘ d ’ value from 0.33 nm to 0.79 nm due to the
complete oxidation and exfoliation of graphite. This is in accordance with earlier reports. 25 The
interlayer spacing of graphene (graphene synthesized by this route) and N-Graphene are larger than that
of graphite. 26 The chemically reduced GO (graphene) possessed a broad peak centered at 23.87 with a
corresponding d -spacing of $ 0.37 nm. However, the hydro- thermally synthesized N-Graphene with
various quantities of ammonium hydroxide (3 to 10 mL) showed pronounced peaks at 24.22, 25.94, 25.7
and 25.7 with corresponding interlayer spacing of 0.36, 0.34, 0.34 and 0.34 nm, respectively. The 3 mL
sample showed the highest crystallinity among all the doped samples. The interlayer spacing was slightly
decreased near to the graphite atomic layer (0.33 nm) with an increasing amount of ammonium
hydroxide ( i.e. from 3 to 10 mL), probably due to the further reduction of RGO. Moreover, it is also
noticeable that increasing the amount of ammonium hydroxide also broadened the graphitic peak
corresponding to the (002) plane, indicating the reduction of crystallinity, and this is in accordance with
earlier reports. 27 Fig. 2 shows the Raman spectra of graphite, GO and N-Graphene. The two typical
peaks in the graphene based materials are observed at 1348 cm À 1 and 1580 cm À 1 referred as the D
and G bands, where the D band shows the presence of defects in the graphitic lattice with A1g
symmetry, while the G band, is asso- ciated with the in-plane E 2g mode of single crystalline graphitic
carbon atoms in the honeycomb lattice. Generally, the I D / I G ratio provides information on the in
plane crystallite dimen- sions, in plane and edge defects and the disorder nature of the graphene
derivatives. It is well documented that the introduction of N atoms into graphene can enhance the
formation of a large quantity of defects resulting in a high intensity D band due to formation of smaller
nanocrystalline graphene domains by heteroatom doping. 28,29 The D and G bands obtained for
graphite clearly indicates the absence of disorder. As shown in Fig. 2, the signi cant increase in the D
band of N-Graphene clearly indicates the defects and disordered structure of N-Graphene. The increase
in the I / I band ratio from 0.95 to 1.10 in the Raman spectra is shown in Fig. 2 and indicates the increase
in defects upon an increase of ammonium hydroxide content. The high I D / I G ratio of N-Graphene
compared to that of pristine graphene clearly demonstrates the large structural defects and edge plane
exposure caused by the insertion of heterogeneous N atoms into the graphene layers. However, there is
not much change in the I D / I G ratio for various N-Graphene, possibly due to merely similar defects
created during di ff erent amounts of N doping. Fourier transform infrared (FT-IR) spectroscopy is an
ideal analytical tool to identify the functional groups present in graphite, the intercalation of GO by
oxidation, graphene and N-Graphene. Fig. 3 shows the typical FT-IR spectra of GO and N-Graphene
prepared in di ff erent ammonium hydroxide content. Two remarkable absorption peaks obtained at
3400 and 1032 cm À 1 clearly indicates the presence of absorbed water molecules and C – O groups,
respectively. The GO exhibits a band at 1725 cm À 1 , which was assigned to the carbonyl (C ] O)
stretching groups. This stretching is pronounced in the GO sample due to higher degree of oxidation and
the strong C – O epoxy group stretching (C – O – C) peak at 1917 cm À 1 , whereas GO shows broad C – O
stretching bands from 1000 to 1400 cm À 1 , indicating the coexistence of O ] C – OH (carboxyl), C – O –
C (epoxy), and C – OH (hydroxyl) groups. It is well known that epoxy and hydroxyl groups exhibit both
edge and basal planes while carboxyl groups are mainly gra ed on the edges of oxidized graphite. 30 In
the plane structure of GO, the peaks at 1571 and 1725 cm À 1 are evident for C ] C and C ] O bands. The
peaks at 3004 and 3434 cm À 1 correspond to C – H and O – H groups. The GO was chemically reduced
by the hydrazine hydrate reduction process. A er the reduction reaction, the peak at 1725 cm À 1
corresponds to the weak and sharp C ] O stretching groups. The GO has been successfully reduced by
hydrazine hydrate to obtain graphene. In N-Graphene, the nitrogen atoms replace carbon atoms. The
peaks appearing at 1187 and 1571 cm À 1 in N-Graphene correspond to the strong and sharp peaks of C
– N and C ] C stretching bonds, respectively (Fig. 3). FE-SEM images of graphite, GO, graphene (GN) and
N-Graphene are shown in Fig. 4. The graphite powder was composed of number of ake-like layers
(Fig. 4a). However, a er the oxidation process, these graphite layers were exfoliated and subsequently
intercalated by epoxy, carboxyl and hydroxyl functional groups. The GN maintained its two dimensional
sheet-like structures as seen in the FE-SEM image (Fig. 4b). The crystalline structure and transparency of
the sheets are clearly maintained in N-Graphene 3 mL and N-Graphene 5 mL (Fig. 4c and d). Surprisingly,
upon increasing the amount of ammonium hydroxide solution, the morphology of the N-Graphene
sheets aggregated during the hydrothermal process and is shown in Fig. 4e and f. The TEM image of the
GO sheet is shown in Fig. 5a and the corresponding Selected Area Electron Di ff raction (SAED) pattern is
shown in Fig. 5a1. A er reduction, a single trans- parent sheet of GN was observed and is shown in the
TEM image (Fig. 5b), and hexagonal rings directly visualized in the SAED pattern, while N-Graphene
appeared like a crumpled sheets as observed in Fig. 5c. The morphology of N-Graphene was destroyed
upon increasing the amount of ammonium hydroxide (>3 mL), and the TEM and corresponding SAED
(Fig. 5d – f) patterns show their amorphous nature, indicating the structural distortion. N-Graphene was
prepared using ammonium hydroxide solution at di ff erent volumes (3 – 10 mL) by a hydrothermal
method. XPS studies con rmed the presence of nitrogen doping in the GN sheets and are shown in
Fig. 6. The XPS results show that with an increase in the amount of ammonium hydroxide from 3 to 10
mL, the amount of N-doping decreased and is shown in Fig. 6. The percentage of nitrogen incorporated
into the GN sheets was found to be highest at 4.5 atomic% for 3 mL of ammonium hydroxide solution
and decreased to 0.9 to 3.0 atomic% when the amount of ammonium hydroxide was increased as shown
in Table 2. The increase in pH as seen in Table 2 indicates that the high alkaline environment is not
advantageous for nitrogen content. 31,32 Fig. 6a shows the survey scan of N-Graphene (3 mL) and it can
be seen that the peaks observed at 284.7, 401 and 532.5 eV correspond to C1s, N1s and O1s,
respectively. The high resolution of N1s scanning spectrum was deconvoluted into four individual
components: pyridinic like N, pyrrolic like N, graphitic like N and pyridinic oxide like N observed at 399.3,
400.1, 401 and 402.2 and 403 eV, respectively (Fig. 6(ii)). Fig. 6(i) shows the high resolution C1s of 3 mL
N-Graphene a er deconvolution into three components, namely, C – N, C – O and C ] O corresponding
to the peaks observed at 285.9, 286.9 and 288.7 eV, respectively. The electrochemical performance
depends on the edge defects on the graphene sheet, like the presence of pyridinic N-Graphene. 33 Here,
the percentage of pyridinic N was very low compared to that of pyrrolic and graphitic N. However, the
high speci c capacitance obtained in the present study is possibly due to the presence of various N-
functionalities. The electrocatalytic activity of N-Graphene was found to be dependent on the graphitic
N-content, which determines the limiting current density, 34 while pyridinic N contributes to the major
part of capacitance increment in N-Graphene among the various N-con gurations. 35 Further,
increasing the volume of ammonium hydroxide leads to a change in the microstructure (interplanar
spacing due to reduction) as well as the crystallinity of the GN (a ff ected adversely as it is seen from the
TEM and SAED studies), which also a ff ect the electrochemical performance of N-Graphene. The limiting
current density proceeds the maximum current density to achieve a desired electrode reaction before
hydrogen or other extraneous ions are dis- charged simultaneously and also without undue interference
such as that from polarization. The high resolution of O1s was obtained at 532 eV (Fig. 6(iii)). Cyclic
voltammetry (CV) and galvanostatic charge – discharge cycling are recognized to be ideal experimental
techniques to evaluate the supercapacitive behavior of any materials. 1,2 Fig. 7a shows the CV curves of
N-Graphene recorded at di ff erent scan rates ranging from 10 to 200 mV s À 1 in an aqueous solution of
1 M H 2 SO 4 within a potential window from À 0.2 to 0.8 V vs. SCE. The rectangular shapes of the
voltammograms exhibit a mirror image of the cathodic and anodic parts, indicating ideal capacitor
behaviour of pristine and N-Graphene. As the sweep rate increases, the voltammetric current increases,
indicating better rate capability and reversibility. Fig. 7b shows the linear variation of current density
with scan rate revealing the surface adsorption – desorption process. The typical galvanostatic charge –
discharge curves recorded for N-Graphene are shown in Fig. 8 at a current density of 1 mA cm À 2 . The
linear variation of potentials with time is additional nger print evidence for capacitive behaviour. 1,2
The highly symmetrical charge – discharge curves indicate excellent electrochemical reversibility during
the charge – discharge process. The speci c capacitance of N-Graphene (3 mL ammonium hydroxide)
was found to be 459 Fg À 1 at a current density of 1 mA cm À 2 , which is several times higher than that
of GN materials and also much larger than the N-Graphene materials previously reported. 19,35,36
Moreover, the speci c capacitance value of N-Graphene obtained in the present method is even
comparable to those of metal oxide/graphene and polymer/ graphene materials. 37 – 41 The speci c
capacitance values for the various types of N sources for N doping used in the literature and the
reported values are shown in Table 1. Fig. 8 shows the variation in speci c capacitance as a function of
N doping and the volume of ammonium hydroxide. The literature indicates that the speci c
capacitance is drastically a ff ected by the amount of N-doping in graphene. 31 But, increasing the
amount of ammonium hydroxide will also a ff ect the structure of GN as it is observed from TEM and
SAED data (Fig. 5). A drastic drop in the capacitance value was observed when the amount of
ammonium hydroxide increased from 3 mL to 5 mL and may be due to the structural distortion, and also
due to the lowering the amount of nitrogen to 0.9 atomic% from 4.5 atomic%. But further increase in
the amount of ammonia solution increases the amount of nitrogen, and hence, though the structural
distortion happened, the amount of nitrogen was increased from 0.9% to 1.7 atomic% when the
ammonia solution is increased from 5 mL to 7 mL. Again, an increase in ammonia from 7 mL to 10 mL
completely amorphized the graphitic backbone and hence though the amount of nitrogen was
increased, its capacitance value was decreased. Moreover, out of the various nitrogen functionalities, it
is reported that pyridinic nitrogen is contributing to the supercapacitance of the resultant doped
structure. 35 The capacitance variation follows the same trend as that of the percentage of pyridinic
nitrogen (inferred from the XPS measurements) present in the samples. This is also in accordance with
earlier reports. 35 In order to understand the rate capability of N-doped graphene, galvanostatic charge
– discharge curves were recorded at di ff erent current densities ranging from 1 to 20 mA cm À 2 . Fig. 9
shows the speci c capacitance of N-Graphene (3 mL) as a function of current density. The speci c
capacitance values of N-Graphene (3 mL) were calculated to be 459, 242, 209, 186 and 186 Fg À 1 at 1,
2, 5, 10 and 20 mA cm À 2 , respectively. The improved speci c capacitance of N-Graphene (3 mL) was
well maintained even at higher current densities. For instance, a speci c capacitance of 186 Fg À 1
could be retained even at 20 mA cm À 2 current density indicating that the N-doping does not lead to
any deterioration from the original power capability of graphene. 36 Evaluation of supercapacitors in
terms of speci c power (SP) and speci c energy (SE) is of practical interest. The values of SP and SE
were calculated using the equations shown below: