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Nitrogen-doped Graphene-like Carbon Nanosheets from Commercial Glue:

Morphology, Phase Evolution and Li-ion Battery Performance

Article  in  Dalton Transactions · July 2018

DOI: 10.1039/C8DT01787E

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Nitrogen-doped Graphene-like Carbon Nanosheets from

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Commercial Glue: Morphology, Phase Evolution and Li-ion Battery
Received 00th January 20xx,
Accepted 00th January 20xx
Performance
DOI: 10.1039/x0xx00000x D. Damodar,a S. Krishna Kumar,b S. K. Martha b and A. S. Deshpande*a
www.rsc.org/ We report a two-step process to synthesize nitrogen-doped graphene-like carbon nanosheets (N-CNS), using commercially
available ethyl cyanoacrylate based super glue as a carbon precursor. In this process, super glue is polymerized in aqueous
NaCl solution, followed by carbonization at 1000 °C. The scanning electron microscopy (SEM) and high resolution
transmission electron microscopy (HRTEM) studies show that the resultant material consists of micron-sized carbon
nanosheets with wrinkled morphology. The HRTEM, X-ray diffraction (XRD), XPS and Raman spectroscopic studies confirm
the formation of nanocrystalline and graphitic, nitrogen doped carbon nanosheets. Detailed FTIR analysis of the
degradation products of the polymeric precursor (polyethyl cyanoacrylate) at various heat treatment temperatures in inert
atmosphere reveals that, the polymer undergoes cyclization process similar to polyacrylonitrile (PAN) during carbonization
to yield the N-CNS. The N-CNS used as an anode for lithium-ion battery shows stable reversible capacities of 480 mAh g-1
for 100 cycles, which indicates that N-CNS are promising material for lithium-ion battery application. In a broader
perspective, unique chemical transformation of polyethyl cyanoacrylate to graphitic carbon may be useful to design new
nanostructured carbons for a plethora of applications.

specific molecular moieties. As a result, the storage capacity of

Introduction carbon nanostructures improves, which is desirable trait for
23
various energy storage applications. However, synthesis of
The Nanostructured materials have generated immense
nitrogen doped carbon nanosheets is still a challenging task. In
interest in various advanced applications like energy storage,
general, synthesis of nitrogen doped carbon nanostructures
purification systems, electronic devices, sensors, actuators and
1-3 can be categorized into two approaches, such as post-
bio-medical applications. Various allotropes of carbon are 23
treatment method and in-situ synthesis method. Post-
commonly used active materials for these applications owing
4-10 treatment processes include direct thermal treatment of
to their unique functional properties. In particular,
carbon nanosheets along with nitrogen containing precursors.
graphene and graphene-like two-dimensional nanosheets with
2 11-16 These methods result in doping of nitrogen only on the surface
sp carbon network possess fascinating properties, such as
and at edges of carbon nanosheets but not through the bulk of
high electron mobility, electrical and thermal conductivity and 23
material.
Young’s modulus. These attractive properties make them quite
15,17,18 In contrast, in situ synthesis processes can yield carbon
useful for various applications. These properties can be
nanostructures with homogeneous incorporation of the
further tailored by doping graphene with other elements such
dopant i.e. nitrogen substitution throughout the bulk of
as B, N, P, and S and altering the size and shape of
19-22 material. Moreover, usage of high quality carbon nanosheets
nanostructures. Particularly, nitrogen doped carbon
as carbon source is not required. Thus, a wide variety of
nanosheets (N-CNS) show significant changes in their
precursors can be used for the synthesis of N-CNS by in situ
functional behavior due to the presence of nitrogen in the 23
synthesis. Using in situ process, high quality N-CNS can be
form of pyridinic-N and pyrrolic-N groups within the hexagonal
produced. For example, N-CNS synthesized using chemical
carbon network. The presence of such functional groups
vapor deposition (CVD) is used in field-effect transistors,
increases the affinity of the carbon material for adsorption of 23
sensors and actuators. However, CVD processes are
expensive as ultra-high purity precursor gases are required for
the growth of N-CNS. Furthermore, CVD is not suitable for
applications such as lithium-ion batteries, super capacitors and
hydrogen storage systems, where large quantities of N-CNS are
23
required. Apart from CVD, methods such as hydrothermal
carbonization followed by chemical activation, segregation-

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growth method, direct pyrolysis of nitrogen containing chloride (NaCl) was obtained from RANKEM India (Analytical
precursor and carbonization of polymers using reagent grade), and deionized (DI) water of having resistivity of
23
inorganic/organic templates are well known approaches for 18.2 MΩ cm was used for preparations of solutions.
N-CNS synthesis. Among these, direct pyrolysis of precursor
method is more attractive approach due to availability of Synthesis
various nitrogen contained precursors and ease of processing. For the synthesis of nitrogen doped carbon nanosheets,
Numerous nitrogen containing materials have been used as the weight ratio of ethyl cyanoacrylate (Fevi kwik®) and NaCl
precursors including, ionic liquids (ILs), polymers and bio- (solution in DI water) was kept fixed at 1:2 for all samples. A
23-25
mass. Finding low cost and abundant nitrogen contained saturated solution of NaCl was prepared by dissolving 33 g
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carbon precursor and optimization of carbonization NaCl in DI water (approximately 92 ml). The saturated solution
temperature are the most important factors in direct pyrolysis of NaCl was added rapidly to 16.5 g cyanoacrylate glue under
of precursor method. Considering these aspects, we present, vigorous stirring. Upon addition, the precursor underwent
the use of ethyl cyanoacrylate as a unique precursor for the rapid exothermic polymerization, resulting in a whitish hard
synthesis of nanocrystalline nitrogen doped graphene-like solid mixture of polyethyl cyanoacrylate and sodium chloride
carbon nanosheets (N-CNS). This is a catalyst-free process, (PECA-NaCl). The resultant mixture was left undisturbed for 24
which involves polymerization of ethyl cyanoacrylate in hours. Next, the excess of NaCl solution was drained off and
aqueous NaCl solution, followed by carbonization in the the hard PECA-NaCl mass was dried at 80 °C for 12 hours. The
presence of salt. Interestingly, during the heat treatment resultant material was then ground to a fine powder. The
process, polymer precursor undergoes structural sample obtained at this stage was labeled as, “as-dried
transformations similar to that seen in case degradation of sample” (PECA-NaCl). The powdered samples were carbonized
polyacrylonitrile (PAN) which involve de-esterification and in tubular furnace at 600 °C, 800 °C and 1000 °C under flowing
cyclization process, resulting in highly graphitic nitrogen doped Argon with a heating rate of 10 °C/min and 1 hour holding
carbon nanosheets. Carbon anode materials like N-CNS have time. Finally, the carbonized powders were washed thoroughly
the potential to deliver stable and high capacity for large with DI to remove NaCl, in order to get nitrogen doped carbon
number of cycles compared to other anodes like Si, SnO2, and nanosheets. The resultant samples were labeled as N-CNS-600,
-1
TiO2 etc. Graphite has the theoretical capacity of 372 mAh g N-CNS-800 and N-CNS-1000, respectively. Additionally, to
with excellent cyclability. However, there is a need of higher understand the role of NaCl in carbon nanosheet formation,
energy and power density carbon to meet the present we prepared a carbon sample following the same protocol as
requirements like electric vehicles and smart grids. N-CNS can that of N-CNS-1000 sample. However, instead of saturated
be one of the efficient contenders with reported capacity as aqueous solution NaCl, we use DI water as an initiator. This
-1
high as 1865 mAh g and provide stable and high energy sample was denoted as CA-1000.
24
density compared to graphite. In general, introducing
heteroatoms like nitrogen can increase the number of active Characterization
sites and can modulate their electronic and chemical Crystallinity of as-dried and carbonized samples was assessed
properties. Thus N-CNS has high electronic conductivity, by X-ray diffraction (XRD) technique, using PANalytical (X’pert PRO)
surface area and good electrochemical stability. These X-ray diffractometer, equipped with Cu – kα radiation (wavelength,
properties of N-CNS make them suitable candidates to be used λ= 1.54 Å) source. To know more about the crystallinity and defect
as anode in lithium-ion batteries. Apart from N-CNS, other density, Raman spectra of samples carbonized at various
nitrogen doped nanostructured materials have also shown temperatures were obtained using Bruker (SENTERRA) micro
promising prospects as anode materials for Li-ion batteries Raman spectrometer with the excitation laser source of wavelength
(LIBs). N-doped carbon nanofibers have shown favorable 532 nm. High resolution transmission electron microscopy (HRTEM)
-1 26
capacity of 637 mAh g (at 2 A/g current density). (JEOL JEM 2100) (operated at 200 kV) and field emission scanning
TM
Hierarchical porous N-doped carbon nanosheets derived from electron microscopy (FESEM) (Carle Zeiss SUPRA 40 ) (operated at
24 -1 -1
silk also show excellent capacity of ~1865 mAh g at 0.1 A g . 20 kV) were used for morphological studies. Carbonized samples
Owing to its potential application in commercial LIB’s, it should were prepared for HRTEM analysis by ultrasonicating the powdered
be produced in bulk with safe and cost effective strategies. samples in ethanol, followed by drop casting of resultant
Here, we present a simple method of synthesizing the N-CNS suspension on to the carbon coated copper grid. Fourier transform
using a household precursor via a simple, cost effective and infra-red spectroscopy (FTIR) (Bruker TENSOR 37) studies were
high yield process. carried out to get insight into mechanism of decomposition of
polymeric precursor. For this, the as-dried PECA-NaCl powdered
samples were heat treated at 160 °C, 300 °C and 400 °C under
Experimental flowing Argon for 1h with a heating rate of 10 °C/min. For FTIR
studies, the as-dried samples and samples heat treated at different
Materials
temperatures were mixed with KBr crystals, ground to a fine
Commercially available ethyl cyanoacrylate (ECA) based powder and pressed into a pellet using pelletizer and FTIR spectra
®
Fevi kwik glue (super glue) (product no: CPFK0.5PP213C-B, were collected in transmission mode. To further examine the
Pedilite, India) was used as a carbon precursor. Sodium chemical content and bonding states, X-ray photoelectron

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spectroscopic (XPS) studies were conducted using ESCA - Omicron

XPS (System with Mg Kα as excitation source). UV Visible spectra of
samples were obtained using PerkinElmer, Lambda 1050
UV/Vis/NIR spectrophotometer. For UV spectroscopy, the samples
were prepared by dispersing carbonized powders in DI water (0.5
mg/25 ml of DI) using ultrasonicator. Thermal analysis of solid
PECA-NaCl mixture was carried by differential scanning calorimetry
(DSC) (DSC 404 F3, Netzsch). DSC analysis of as-dried PECA-NaCl
sample was done under Argon atmosphere, with scan temperature
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range from room temperature to 1000 °C and 10 °C/min heating
rate. BET surface area measurement of carbonized samples was
TM
carried with Quantachrome® ASiQwin (degassing at 300 °C for 4
hrs). The electrochemical measurement of the electrode comprising
N-CNS-1000 powder as active mass was evaluated using Swagelok Fig. 1 FESEM images of (a) as-dried sample (PECA-NaCl) (b) sample carbonized at
cells with a polyethylene-polypropylene trilayer separator (Celgard, 1000°C/ 1h in flowing argon gas and (c) low magnification and (d) intermediate
Inc., Canada). The composite electrode comprised slurry of 90% magnification images of carbonized samples after washing with DI water (N-CNS-1000)
active material, 10% PVDF (Kynar, Japan) in N methyl pyrollidone which show that washing with DI water leads to removal of NaCl leaving behind carbon
nanosheets organized in sponge-like morphology.
(Aldrich), were coated on to copper foil (>99.9%, Strem chemicals,
Inc, US) current collector using doctor blade technique. The
polymerization process tends to be very low, we decided to
composite electrodes were dried under vacuum at 90 °C followed
carry out the polymerization reaction in aqueous medium to
punched into 1cm diameter electrodes. The active masses of the -
improve the polymer yield. Though Cl ions are stronger
electrodes are about 5 mg cm-2. Li foils (Alfa Aesar) were used as
nucleophiles as compared to H2O, both species can initiate
counter electrodes. The electrolyte solution used is 1M LiPF6 in 1:1
polymerization of ethyl cyanoacrylate in aqueous medium.
mixture of EC and DMC (Merck). Cyclic voltammetric study and
Therefore, saturated solution of NaCl was used in order to
Galvanostatic charge–discharge cycling was carried out using a -
maintain high effective concentration of Cl ions. During the
multichannel battery tester (Arbin BT2000 - Battery Test
synthesis process, the liquid monomer was mixed rapidly with
Equipment, USA) within the operating voltage range of 2.5 to 0.01 V
saturated NaCl solution, which resulted in rapid polymerization
at various rates The impedance measurements were carried out
of monomer. Polymerization was followed by aging,
in a frequency range between 1 MHz and 10 mHz in fully
decantation of NaCl solution and drying process. The as-dried
discharged condition (SoC 0) after 40 cycles at 2.3 V (2 h rest
polymer was characterized by FTIR spectroscopy, XRD and SEM
after charging to 3 V).
analysis. FTIR spectrum of as-dried PECA (Poly ethyl
cyanoacrylate)-NaCl sample (Fig. S1a) shows all the
characteristic IR active vibrational modes of PECA reported in
Results and Discussion 31,32,33
the literature. No peaks corresponding to ECA monomer
Structural and functional properties of carbon based materials, were seen, which confirms that the sample is completely
especially nitrogen doped carbons, are profoundly affected by polymerized.
the choice of carbon precursors and the methods of Crystallinity of as-dried sample was assessed by powder
27,28
preparation. In particular, the properties of nitrogen XRD. The XRD pattern of as-dried polymer (Fig. S1b) shows
containing carbon precursor such as their primary structure, high intensity, sharp reflections corresponding to standard
molecular weight and degradation mechanism has been NaCl pattern (JCPDS No: 050628). Absence of any other
shown to influences the morphology, crystal phase evolution reflections points out that PECA is in amorphous form.
and extent of doping in resultant carbon materials. After Furthermore, presence of NaCl reflections indicates that,
careful consideration of these points, we selected ethyl though all the NaCl solution was decanted before the drying
cyanoacrylate as a carbon precursor. Commercial superglues process, some NaCl got incorporated within polymer matrix.
which contain ~99.5% pure ethyl cyanoacrylate monomers are This may be due to retention of NaCl solution within the
readily available. The monomer unit contains nitrile group polymer network followed by recrystallization of NaCl crystals
which makes it a suitable precursor for the synthesis of N- during the drying process. Homogeneous incorporation of NaCl
29
doped carbons via direct synthesis approach. Ethyl with polymer matrix was further evident from scanning
cyanoacrylate can be readily polymerized by variety of electron microscopy (SEM). Low magnification SEM images of
initiators including neutral, anionic and radical initiators. as-dried sample (Fig. 1a) show particles having broad size
Polymerization of alkyl cyanoacrylates has been studied in distribution ranging from sub-micron sized particles to 100 µm
detail and reports show that, the choice of initiator dictates sized particles. The as-dried samples were carbonized at 1000
polymerization rate, molecular weight, degradation and most °C in argon atmosphere. Since the melting point of NaCl is 801
30,31
importantly morphology. Considering this, we selected °C, at the carbonization temperature (1000 °C) NaCl is present
NaCl as an initiator for polymerization of ethyl cyanoacrylate in molten form and recrystallizes from the melt upon cooling.
due to its low cost, non-toxic nature and chemical stability at Fig. 1b shows the morphology of sample after carbonization.
high temperature. As the yield of polymer via vapor phase

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Fig. 3 (a) XRD pattern of N-CNS-1000 sample showing broad reflections corresponding
to graphitic carbon along with sharp reflections corresponding to NaCl and (b) Raman
spectrum of N-CNS-1000.

shows wide sheets having dimensions in the range 5-10 µm.

Well defined rectangular pores generated due to the removal
of trapped NaCl crystals in the nanosheets are clearly seen
along with smaller pores. The selected area electron
Fig. 2 FESEM of N-CNS-1000 at (a) intermediate magnification image showing diffraction (SAED) pattern (Fig. 2c inset) shows a diffused ring
wrinkled carbon nanosheets and (b) and higher magnification showing surface pattern which indicates that the carbon nanosheets are
porosity. HRTEM images of N-CNS-1000 at (c) low magnification indicating well
nanocrystalline in nature. The higher magnification HRTEM
defined pores. SAED pattern (Inset) shows ring pattern (002) and (101) reflections
corresponding to polycrystalline graphitic phase (d) High magnification image of
images of N-CNS-1000 (see Fig. 2d) taken from the edge part
carbon nanosheets showing lattice fringes with regular periodic spacing. reveals the distinct layered stacking with short range ordering
(buckled structure) The interlayer spacing was found to be
Compared to as-dried samples, particle size reduced to less 0.34 ± 0.03 nm (based on 250 measurements), which is slightly
than few microns and very few larger particles were seen. larger than the interlayer distance of graphitic carbon (0.335
After carbonization, the samples were washed to remove nm).8 The increased d-spacing might be attributed to the
NaCl. The SEM image of washed samples (N-CNS-1000) (Fig. topological defects induced due to nitrogen doping.
1c) shows that removal of NaCl leads to sponge-like porous Though HRTEM results show that N-CNS-1000 samples
structure. The intermediate magnification image of this sample exhibit good crystallinity, the information obtained is
(Fig. 1d), reveals that the sponge-like structures consist of restricted to locally observed morphology and crystallinity, for
aggregates of graphene-like wrinkled carbon sheets. At higher a small amount of sample. On the other hand, XRD technique
magnification (Fig. 2a, b), we see that the surface of these thin gives information on long range ordering over large sample
sheets is flecked with pore of sizes smaller than 50 nm. Such volume. Thus to assess the crystallinity of the bulk of sample,
pores may result due to shrinkage which place during XRD studies of N-CNS-1000 were carried out. The XRD pattern
decomposition and crystallization process during the of N-CNS-1000 sample (Fig. 3a) shows reflections centered at
transformation of PECA to carbon nanosheets. It is well known 25.33° and 43.12 that can be ascribed to the (002) and (101)
that substitution of nitrogen atoms in place of carbon atoms in reflections of graphitic carbon, respectively.36 The broad
graphene leads to topological defects in graphene.
34,35
Thus, nature of the reflection corresponding to carbon indicates that
the smaller pores and the wrinkling effect can be attributed to N-CNS-1000 sample is nanocrystalline in nature. The interlayer
nitrogen doping of carbon sheets. Occasionally, larger distance “d” of (002) plane obtained using Bragg’s law, is ~
rectangular pores are also seen. These pores are clear 0.35 nm which is larger than the d-spacing of standard
indication that, the NaCl crystals are embedded within the graphite and is in agreement with HRTEM results (lattice
carbon matrix and which are removed during washing process spacing ~ 0.34 nm). The literature reports show similar
leaving behind well-defined pores. The as-dried samples were increase in d-spacing in case of few layer graphene materials.37
also carbonized at temperatures below the melting point of It has also been reported in case nitrogen doped carbons that,
NaCl (600-800 °C). SEM images of these samples (N-CNS-600 lattice parameter increases due to substitution of carbon
and N-CNS-800) (Fig. S2) show the distinct carbon nanosheet atoms with nitrogen atoms in carbon framework. Nitrogen
morphology similar to 1000 °C carbonized samples. This doping also results in introduction of defects in carbon
38,39
indicates that NaCl in molten state is not necessary for the framework which leads to increase in d-spacing.
formation of carbon nanosheets. The thickness of N-CNS-600, Additionally, sharp reflections corresponding to NaCl were also
N-CNS-800 and N-CNS-1000 samples was found to be 6.33 ± seen in XRD pattern of N-CNS-1000 sample, which indicates
0.9 nm, 6.16 ± 1.0 nm and 6.23 ± 1.0 nm, respectively (based that, even after thorough washing, NaCl still remains within
on 50 measurements per sample). This indicates that carbon nanosheets matrix. This shows that, small amount NaCl
carbonization temperature has very little effect on the crystals may be trapped within tightly folded carbon
thickness of carbon nanosheets. The transmission electron nanosheet, which makes it difficult to eliminate them
microscopy (TEM) images of carbonized samples are consistent completely by washing.
with the FESEM results, the low magnification image (Fig. 2c)

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Fig. 5 FTIR spectra of PECA-NaCl sample, carbonized at various temperatures.
Fig. 4 Survey scanned XPS spectrum (a) and fine scanned spectra of Cs1s (b), N1s (c)
and O1s (d) of N-CNS-1000.
formation of graphene-like carbon nanosheets.44 Thus, based
on above discussion, it is clear that Raman and UV-Vis
Raman spectrum of graphene-like nitrogen doped carbon
spectroscopy results are consistence with the HRTEM and XRD
nanosheets (N-CNS-1000) (shown in Fig. 3b) shows two major
-1 -1 results, confirming the nanocrystalline, graphitic nature in N-
bands positioned at 1580 cm and 1350 cm . These bands
CNS and nitrogen doping induced defect structure.
correspond to G-band and D-band respectively of graphitic
To further assess the elemental composition of carbon
carbon with the ID/IG ratio of 0.93. The shift in the peak
nanosheets, nature of bonding and structural evolution, XPS
position of G-band towards to higher frequency is an
studies were conducted on samples carbonized at 600 °C, 800
indication for existence of nanocrystalline domains, i.e. smaller
2 40-43 °C and 1000 °C. Fig. 4a shows, full scan XPS spectrum of N-
in-plane sp domains. In addition to nanocrystalline nature,
CNS-1000 sample with three characteristic peaks at 284 eV,
nitrogen doped carbons also show blue shift in peak position
401 eV and 532 eV that correspond to C1s, N1s and O1s,
of G-band. Nitrogen doping also leads to generation of
respectively.45,46 The amount of carbon, nitrogen and oxygen
topological defects which results in increase in D band
40 in N-CNS-1000 are 93.23%, 2.67% and 4.13%, respectively. The
intensity. Apart from D and G bands three broad and low
-1 deconvoluted C1s spectrum of carbon nanosheets (Fig. 4b)
intensity bands in the range of 2600-3200 cm are also seen in
shows well fitted peaks around 284 eV, 286 eV, 288 eV and
Raman spectrum of N-CNS-1000 sample (Fig. 3b). These bands
-1 -1 290 eV which belong to C=C (sp2 C), C=N, N-C=O and π-π*
can be ascribed to 2D (2710cm ) and D” (3200 cm ) bands
-1 satellite peak which is a signature peak for graphitic sp2 C,
and defect related D + G band (2920 cm ). These bands are
2 respectively. Thus it is evident from C1s spectrum of N-CNS-
characteristic of sp graphitic carbons. Reports show that,
1000 sample that carbon exists in the graphitic form. The fine
reduction in crystallite size, doping and structural defects for
scan N1s spectrum of N-CNS-1000 (Fig. 4c) shows presence of
graphitic carbon result in reduction in peak intensity and peak 2
sp nitrogen containing functional groups such as pyridinic-N
broadening of 2D peaks as seen in case of N-CNS-1000
41 (N-P) (~ 397 eV), pyrrolic-N (N-5) (~399 eV), pyridonic -N (N-X)
sample. Similar Raman spectra were observed in case of N-
(~ 400 eV) and quaternary-N (N-Q) (~ 401 eV). All these groups
CNS-600 and N-CNS-800 (see Fig. S4) with ID/IG ratios of 0.67
have nitrogen as a part of 5 or 6 membered rings, which shows
and 0.88, respectively. As the carbonization temperature is
that nitrogen atoms are located within the graphitic carbon
increased, more number of nitrogen atoms are eliminated
network. Typically, nitrogen in, N-5, N-X, N-6 form is
from the hexagonal network, which leads to introduction of
responsible for creation of structural defects i.e. pores in
additional defects in carbon network and increase in porosity. 46
hexagonal network of carbon. Introduction of pores within
Thus, higher carbonization temperature leads to higher ID/IG
carbon framework lead to increase in the number of
for N-CNS-1000 (ID/IG = 0.93) as compared N-CNS-600 and N-
unsaturated carbon atoms placed at edge positions. These
CNS-800 samples. Increase in the intensity of 2D band from N-
unsaturated carbon atoms are prone to oxidation when
CNS-600 to N-CNS-1000 also indicates enhanced graphitization 47
exposed to atmospheric oxygen. Consequently, we see peaks
with increase in carbonization temperature. Additionally, UV-
corresponding to oxygen functional groups for sample
Vis spectrum of N-CNS-1000 (see in Fig. S5) shows sharp
-1 carbonized at 1000 °C. Fig. 4d shows the O1s spectrum of N-
absorption peak around 265 cm which is attributed to the π-
CNS-1000 sample with peaks at 530 eV, 532 eV and 534 eV
π* transition of carbon-carbon double bonds. This spectrum is
which belong to O=C-OH, C=O and C-OH, respectively. The
consistent with absorption range of graphene and graphene-
chemical and structural changes are reflected in BET surface
like carbon nanomaterials and it is a clear evidence for the
area values of N-CNS-600, N-CNS-800 and N-CNS-1000 are 73

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-1 -1
cm ) and C-O (1255 cm ) decreased drastically. This indicates
that at 300 °C de-esterification i.e. the elimination of ester side
of group (-COOC2H5) of PECA backbone takes place to a
significant extent. Further we also see decrease in intensity of
-1
peak at 2250 cm which corresponds to C≡N group, however,
-1
the intensity of peak at 1620 cm (C=C, C=N) increases and
-1
new peak around 1261 cm (C-N, C-C) appears. In addition,
-1 -1 -1
peaks at 1095 cm , 1024 cm and 805 cm (=C-H bending)
48,49
which correspond to heteroatomic aromatic ring structure
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also appear. These changes in FTIR spectra of 160 and 300 °C
Scheme 1. Possible mechanism for ladder structure formation during heat treatment (< heat treated samples are very peculiar. Similar changes in FTIR
600°C) of poly ethyl cyanoacrylate under inert atmosphere.
spectra of polyacrylonitrile (PAN) fibers heat treated at similar
2 -1 2 -1 2 -1
temperature range were also observed.33 Houtz, et al.,
m g , 59 m g and 169 m g , respectively. Slight decrease in proposed that during decomposition of PAN the polymer
surface area from N-CNS-600 to N-CNS-800 is due to increase chains undergo cyclization process which involves adjacent
in graphitization. Whereas as large increase in surface area of C≡N side group. During cyclizaƟon C≡N gets converted to C=N
N-CNS-1000 can be attributed to the loss of nitrogen and other resulting in six membered pyridine like ring structure.
functional groups. Consequently, the aliphatic polymeric chains transform into
In order to follow the structural evolution of carbon cyclic “ladder polymer”. In addition, reports show that during
network with heat treatment temperature, the XPS data of degradation of PAN fibers dehydrogenation reaction also takes
samples carbonized at 600 °C (N-CNS-600) and 800 °C (N-CNS- place which stabilizes the polymer backbone through
800) was compared with sample carbonized at 1000 °C. Fig. S6 formation of double bonds.50 By comparing our data with
provides fine scanned XPS spectra of C1s, N1s and O1s of reports on PAN fiber decomposition studies, we believe that in
samples calcined at different temperature. It can be seen that, thermal degradation of as-dried samples, PECA undergoes
with increase in carbonization temperature, there is notable cyclization similar to that of PAN as evident from noticeable
increase in carbon content and decrease in oxygen content, decrease in intensity of peak C≡N (2250 cm-1), increase in
whereas nitrogen content decreases only marginally (Fig. S6). intensity of peak of C=C/C=N (1620 cm-1) and appearance of C-
Furthermore, N1s and C1s spectra of CNS samples carbonized N peak (1260 cm-1). Dehydrogenation process was also evident
at 600 °C and 800 °C (Fig. S6) show peaks corresponding to sp2 from appearance of 1620 cm-1 (C=C), 1095 cm-1 and 1024 cm-1
nitrogen and sp2 carbon containing functional groups similar to peaks. The FTIR spectra of 600 °C heat treated sample shows
sample carbonized at 1000 °C. Absence of peaks corresponding that peaks for C=O and C≡N disappears completely, whereas
to sp3 nitrogen or sp3 carbon clearly shows that even at low peaks for C=C/C=N, C-N and peaks corresponding to
carbonization temperatures nitrogen containing carbon exists heteroatomic aromatic ring structure become most
in the form of network similar to graphitic carbon structure. prominent. This indicates that at 600 °C PECA undergoes de-
In addition to XPS studies, FTIR also gives valuable insight esterification and cyclization process to a larger extent. As
into molecular structure of the materials. Therefore, FTIR discussed earlier, N1s XPS spectrum of 600 °C shows that sp3
studies were performed to understand the chemical nitrogen containing groups are absent and nitrogen exists only
transformation and structural changes happening during in the form of cyclic functional groups such as pyridinic-N (N-P)
carbonization of as-dried precursor. In order to determine and pyrrolic-N (N-5). This further supports the evidence
temperature points at which the sample undergoes obtained from FTIR that cyclization process is complete by 600
decomposition/ structural transformation, Differential °C. Furthermore, C1s spectrum of 600 °C sample (supporting
scanning calorimetry (DSC) of as-dried samples was done information Fig. S6) shows that major fraction of carbon exists
under Ar gas flow. The DSC analysis of as-dried sample (see in C=C-H form (283.8 eV) along with C=C (284 eV) with very
Fig. S8) shows an endothermic reaction in the range of 150- small fraction of C=O (288 eV) functional group. This indicates
300 °C with maximum heat absorption at 235 °C. Thereafter no that the de-esterification process and dehydrogenation
significant heat flow was observed till 600 °C. Therefore, in process also occurs to a great extent by 600 °C.
order to analyze chemical changes during the decomposition Thus, drawing parallel from degradation of PAN, a
we selected 160 °C, 300 °C, 600 °C, 800 °C and 1000 °C as the proposed mechanism is schematically shown in Scheme 1,
reference points for FTIR analysis. Comparison of FTIR spectra which shows that formation of ladder structure may result in
for as-dried and all the heat treated samples are shown in Fig. three possible ways (i) de-esterification followed by
5. It can be seen that the FTIR spectra of as-dried and sample cyclization, (ii) cyclization followed by de-esterification and (iii)
heat treated at 160 °C are quite similar except for minor simultaneous de-esterification and cyclization. Reports show
change in the intensity of characteristic peaks of PECA. This that in case of PAN, sequence of cyclization and
implies that, the polymeric precursor does not undergo any dehydrogenation process depends on the heat treatment
change in its chemical composition till 160°C. At 300 °C, the environment conditions i.e. oxidative, reductive or neutral gas
intensity of peaks corresponding to –CH2, -CH3 (2800-2990 cm- environment.
51
Based on the FTIR and XPS studies we
1
for C-H stretch, 1000-1470 cm-1 for C-H bending), C=O (1746 anticipate that, for the heat treatment protocol we followed,

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Fig. 6 (a) Capacity vs. cycle number plot for the N-CNS composite electrodes. Initial 2 cycles at C/10 rate, followed by charge-discharge at 1C rate for 100 cycles; (b) Lithiation and
delithiation voltage profiles for the N-CNS composite electrodes during 1, 2 and 100th cycles; (c) C rate performance for the N-CNS composite electrode at 1C, 2C and 5C rate (as
indicated) during 22 cycles at 25oC. Initial 2 cycles are not presented here.

the ladder structure formation might be taking place by mAh g-1 and a reversible capacity of 480 mAh g-1 during
simultaneous de-esterification and cyclization process. charging. High irreversible capacity is due to formation of SEI
Comparison of FTIR spectra of 600 °C, 800°C and 1000 °C layer during the first cycle. The synthesis method helps in the
shows that intensity of C=N/ C=C (1620 cm-1) and C-N (1261 formation of the N-CNS with highly folded morphology (Fig.
cm-1) decreases which indicates elimination of nitrogen from 2a) and more curled edges which generate lot of cavities.
the sample which is consistent with reduction in atomic These cavities may act as reservoirs for accommodating high
percentage of nitrogen as obtained from analysis of N1s XPS lithium content which is responsible for high capacity of N-
spectra of these samples (Fig. S7). Similar reduction in nitrogen CNS. N-CNS-1000 shows excellent cycling stability with the
content was also observed in case of carbonization of PAN average capacity of 480 mAh g-1. There is a flat plateau in the
fibers, where the reduction in nitrogen content is attributed to first discharge profile in Fig. 6b which may be due to the
elimination of nitrogen during crosslinking between ladder interaction of Li-ion with chloride ion of trace amount of NaCl
structures to yield graphite-like layered structure.51 which is trapped in the N-CNS (during synthesis) and is not
Additionally, the intensity of =C-H (805 cm-1) also decreases removed while washing N-CNS with water. The plateau almost
from 600-1000 °C which is consistent with reduction in disappeared during 2nd cycle indicates the irreversibility of LiCl.
contribution from C=C-H peak (283.8 eV) seen in C1s XPS Fig. 6c shows the galvanostatic charge-discharge capacities at
spectra of these samples.52 In summary, FTIR data along different rates. The Fig. 6c shows the average reversible
supported with XPS results shows that during the heat capacity of 480 mAh g-1 can be obtained at 1C rate, and even
treatment in inert atmosphere till 1000 °C, polymer precursor the cells deliver an excellent capacity of 460 mAh g-1 at 2C and
undergoes concurrently through cyclization and de- 440 mAh g-1 at 5C rate. From the foregoing discussion it is clear
esterification, followed by formation of graphite-like layered that N-CNS synthesized by polymerization of Fevi kwik® shows
structure and finally resulting in formation of nitrogen doped excellent electrochemical performance than that of graphite.
graphene-like carbon nanosheets. For comparison, the electrochemical performance of N-
Cyclic-Voltammetric study of N-CNS-1000 was carried out CNS-800, N-CNS-600 and CA-1000 was also carried out. It can
to assess the redox behaviour of nitrogen-doped carbon be clearly observed from the Fig.S10, that N-doped graphene-
nanosheets (Fig. S9). The broad reduction peak starting from like carbon nano-sheets calcined at 1000 oC (N-CNS-1000)
0.8 V to 0.36 V corresponds to the formation of solid shows improved electrochemical performance compared to
electrolyte interphase (SEI) and the peak vanishes in the the corresponding sample calcined at 800 oC (N-CNS-800) and
successive cycles. The peak close to 0 V corresponds to Li- 600 oC (N-CNS-600). It is also observed that 800 oC calcined
intercalation in carbon anodes. The difference in the area of material shows 12% improvement in electrochemical
o
two curves is equivalent to irreversible capacity or capacity performance than 600 C calcined material. The sample
nd st o
loss in 2 cycle which is due to the formation of SEI in the 1 prepared without NaCl and carbonized at 1000 C (CA-1000)
-1
cycle where lot of Li-ions are consumed. Based on the CV shows reasonably high initial discharge capacity (662 mAh g at
-1
studies, the electrochemical behavior of N-CNS-1000 as anode 0.1C) and charge capacity (456 mAh g at 0.1C), however, the
in lithium batteries were assessed by constant current charge- initial cycle performance of CA-1000 samples is still less
discharge cycling in the voltage range from 2.5 V to 0.01 V at compared to N-CNS-1000 sample. Further, CA-1000 shows
various C rates as shown in Fig. 6. These cells show excellent rapid capacity fading with successive cycles. The improved
-1
cyclability of > 480 mAh g at 1C rate as shown in Fig. 6a. The electrochemical performance is attributed to better
charge-discharge voltage profiles of N-CNS composite anode in graphitization observed for N-CNS-1000 compared to all the
st nd th
the 1 , 2 and 100 cycle are shown in Fig. 6b. N-CNS other samples. Additionally, presence of pores formed by
composite anodes deliver an initial discharge capacity of 1052 highly folded morphology and more curled edges. It is also

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observed that on increasing the carbonization temperature the nanosheets show that, NaCl acts as a hard template for
porosity of the material increases which is responsible for the deposition of precursor material which converts to thick
o
improvement in electrochemical performance of 1000 C carbon nanosheets upon carbonization below melting point of
o o 54
calcined material compared to 800 C and 600 C calcined NaCl. In our case, if NaCl crystals were acting as a hard
sample. Whereas the sample without NaCl which is devoid of template, we should see distinct difference in the morphology
nanostructured features , shows less graphitization and lacks of samples carbonized below and above melting point of NaCl.
the voids and pores which makes complex path for the Li-ion However, we do not see such differences. Hence, we believe
de/intercalation due to which there is rapid capacity fade. that NaCl does not act as a passive template in our case. Thus
The lithium ion battery performance also depends on the based on the current results, the exact role in the formation of
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internal resistance of the cell which in turn depends on nature carbon nanosheets is still obscure. We are carrying out further
of the electrode material and stable SEI layer formation. To studies to know the exact role of NaCl and mechanism of
assess the internal conductivity, electrochemical impedance formation of carbon nanosheets.
studies were carried out 40 cycles. Impedance is the indirect
way of expressing the conductivity. N-doped graphene-like
o
carbon nano-sheets carbonized with NaCl at 1000 C (N-CNS- Conclusion
2
1000) showed low ohomic (6.9 ohm.cm ) and charge transfer To summarize, we presented use of commercially available
2
resistance (Rct - 109 ohm.cm ) compared to material ethyl cyanoacrylate based super glue as a unique precursor for
o 2 o
carbonized at 800 C (Rct – 135 ohm.cm ) and 600 C (Rct – the synthesis of nanocrystalline nitrogen doped graphene-like
2
152.52 ohm.cm ). Whereas the material carbonized without carbon nanosheets (N-CNS). This catalyst-free process involved
NaCl is (CA-1000) showed high charge transfer (Rct – 155 polymerization of ethyl cyanoacrylate in aqueous NaCl
2
ohm.cm ). The low charge transfer resistance of material solution, followed by carbonization of resultant polymeric
calcined with NaCl is attributed to the formation of more mass in the presence of salt at 1000°C. Detailed spectroscopic
ordered structure due to presence of NaCl. The above analysis of the degradation products of polymeric precursor at
observation suggest that the N-CNS-1000 improved various heat treatment temperatures in inert atmosphere
conductivity compared to N-CNS-600, N-CNS-800 and CA-1000. reveals that, polymer precursor undergoes structural
Apart from acting as an initiator we wanted to understand transformations similar to that seen in case degradation of
if NaCl plays any role in the formation of carbon nanosheets. polyacrylonitrile (PAN) involving de-esterification and
Therefore, we carried out the polymerization of ethyl cyclization process. The result of this peculiar degradation
cyanoacrylate in the absence of NaCl i.e. we used DI water behavior is, nanocrystalline, graphitic, nitrogen doped carbon
rather than saturated aqueous solution of NaCl for the nanosheets. N-CNS used as anodes for lithium battery showed
polymerization process. The polymeric material upon -1
stable reversible capacities of 480 mAh g (1C rate) for 100
carbonization (CA-1000) did not show nanosheet like cycles. These results indicate that N-CNS could be used as a
morphology (see Fig. S3). Additionally, High resolution promising anode material for next generation lithium ion
transmission electron microscopy studies of this carbonized batteries. We believe that, unique way in which PECA
sample revealed (Fig. S3c) lack of long range ordering. undergoes structural transformation during carbonization can
However, nano sized domains with short range order with be useful to design new nanostructured graphitic carbons for a
interlayer spacing of d ≈ 0.38 ± 0.05 nm (based on 250 wide range of other applications including energy storage,
measurements) were observed. These features of bulk carbon sensors and catalysis.
sample are similar to the turbostratic carbon but dissimilar
from the carbon nanosheets (N-CNS) prepared through salt
mediated process. So it is clear that NaCl does play a role in
the formation of carbon nanosheets. Throughout the study, Conflicts of interest
we also saw indications that NaCl may be acting as structure The authors declare no conflict of interest.
directing agent in the formation of carbon nanosheets. For
example, rectangular nanopores in carbon nanosheets as
observed in SEM and TEM images suggest that presence NaCl Acknowledgements
crystals in polymerized samples may not be merely due to
recrystallization from trapped solution during drying process. We are grateful Dr. Srinivasan Anandan (Senior Scientist, ARCI,
53
Liu et al. used a deep eutectic salt composition of LiCl/KCl Hyderabad, India) for carrying out XPS spectroscopic studies of
with low melting point. They state that molten salt acts as a carbon samples. We thank IIT Hyderabad and MHRD for
“solvent” which allows dissolution and precipitation of carbon financial support.
in the form of nanosheets. However, in our case, SEM images
of samples carbonized at 600 °C and 800 °C (N-CNS-600 and N-
CNS-800) (Fig. S2) show distinct carbon nanosheet morphology
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Table of Contents
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Morphology of nitrogen doped graphene-like carbon nanosheets along with proposed
mechanism for ladder structure formation during carbonization of commercial glue.

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