Electrochimica Acta 318 (2019) 290e301

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Mesoporous nitrogen-doped carbon@graphene nanosheets as ultra-

stable anode for lithium-ion batteries e Melamine as surface modifier
than nitrogen source
Sampath Gayathri, Paulraj Arunkumar, Eui Joong Kim, Sumin Kim, Inji Kang,
Jong Hun Han*
Nanocarbon Convergence Materials Lab, School of Chemical Engineering, And Optoelectronic Convergence Research Center, Chonnam National University,
300 Yongbong-dong, Buk-gu, Gwangju, 61186, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Nitrogen-doped carbon materials are highly appealing next-generation anode for Li-ion battery owing to
Received 23 March 2019 high energy density, conducting and porous structure, and a large number of ion-binding sites. However,
Received in revised form the formation of micropores limits the ion/electrolyte diffusion at high discharge rate leading to un-
26 May 2019
derutilization of active material, capacity fading, and low cycle stability, hindering their practical
Accepted 7 June 2019
Available online 12 June 2019
application. Herein, we report mesoporous-rich carbon hybrid comprising of zeolitic imidazolate
framework (ZIF)-derived nitrogen-doped carbon-anchored graphene using melamine as the surface
modifier and pore expander. A high specific capacity of 775 (after 1100 cycles) and 675 mAh g
1 (after
1000 cycles) were obtained at current densities of 1000 and 2000 mA g
1 (4C) which is two-fold higher
than the initial capacity. The melamine-modified anode exhibited excellent cycle retention of 163% at
1000 mA g
1 after 800 cycles, compared to 91% for the unmodified anode, indicating the activation
process through the mesoporous channels. Superior cycle retention and long cycle life were attributed to
the melamine-induced features viz mesoporous structure and defective sites formed on carbon/graphene
facilitating efficient electrolyte percolation/ion transport and Li-ion storage, respectively. This strategy
provides a promising approach for the design of ZIFs-derived carbon materials for high-performance Li-
ion batteries.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction promising candidate for LIBs to replace commercial graphite anode

Lithium-ion batteries (LIBs) being the most promising energy
storage device for applications ranging portable electronic devices
namely smartphones, laptops, and electric vehicles, owing to high
energy density, long cycle life, and low self-discharge [1,2]. Despite
these, there are still many challenges hindering their practical ap-
plications in hybrid electric vehicles in terms of low energy and
power densities, and safety concerns. The current commercially
available anode in LIBs is graphite with a specific capacity of
372 mAh g
1, however graphite unable to meet the growing de-
mand for LIBs requiring high power densities, superior rate per-
formance, and long cycle life [3]. In this context, researchers have
paid attention to analogous carbonaceous material, as the
* Corresponding author.
E-mail address: jhhan@chonnam.ac.kr (J.H. Han).
due to high specific capacity and fast charge/discharge cycles. The
electrochemical performance of the carbonaceous material has
been greatly improved by heteroatom doping (nitrogen, boron,
phosphorous, sulphur, oxygen), desirable morphology, micro/
nanostructure, and porous network [4,5]. Heteroatom-doping of
carbon offers high electronic conductivity, excellent ionic mobility,
active binding sites, and high specific capacity [6]. Although,
limited rate capability of carbonaceous anode has been addressed
via heteroatom-doping and porous network, their practical appli-
cation is still a big concern due to poor capacity retention and cycle
stability in the battery technology particularly for hybrid electric
vehicular application.
Zhu Li et al. [7] demonstrated that mesoporous architecture is
beneficial for enhancing the capacity retention and specific ca-
pacity via facilitating the ionic/electrolyte transport through
shortened diffusion path length and as a reservoir for ion storage.
The nitrogen-rich porous carbon anode with bimodal mesopore

https://doi.org/10.1016/j.electacta.2019.06.054
0013-4686/© 2019 Elsevier Ltd. All rights reserved.
 S. Gayathri et al. / Electrochimica Acta 318 (2019) 290e301
derived from porous cellular foam silica template, has been re-
ported with high reversible capacity of 1780 mAh g
1 at 100 mA g
1
[8e10]. Nevertheless, it is still a challenge to synthesize a carbo-
naceous material with high electrochemical performance through a
good combination of mesoporous structure, nitrogen doping, with
a good degree of graphitization.
Recently, a unique porous structure in carbonaceous material
was derived from carbonization of metal-organic frameworks
explicitly zeolitic imidazolate frameworks (ZIFs), exhibited inter-
esting properties for energy storage application, which includes
large nitrogen content, high electronic conductivity, and large
surface area [11]. Nevertheless, the ZIF-derived nitrogen-doped
carbon (usually from Zn-containing ZIF-8) lead to micropore for-
mation which is too small for ion transport and electrolyte perco-
lation leading to capacity fading and poor cyclability particularly at
high discharge rates. Therefore, it is vital to increase its pore size for
enhancing energy storage capacity of carbon material. Guan et al.
reported increase in the pore size of ZIF-8-derived porous carbon,
by embedding C60 molecule, that delivers a capacity of 1077 mAh
g
1 at 1000 mA g
1 after 400 cycles [11]. Nevertheless, this
approach involves toxic acid washing and energy intensive Soxhlet-
extraction using organic solvent for long period. Thus, it is imper-
ative to search for a pore-directing additive, which also act as pore
expander for the micropore-rich porous carbon-derived from ZIF.
This pore expansion would eventually enhance Li storage perfor-
mance through optimized pore size [7,12], increased surface area
[13e15], thus improving the structural stability and electronic
conductivity, promoting rapid charge transfer with prolonged cycle
life [16,17]. Hence, a rational choice of harmless pore-directing
agent which can form a desirable morphology and nanostructure,
along with cost-effective green synthesis and capacity to industrial
scale up, can significantly improve the electrochemical perfor-
mance of LIBs.
Herein, we report a facile synthetic strategy to fabricate
mesoporous-rich carbon hybrid derived from ZIF-8 precursor using
melamine as pore expander and surface modifier. Mesoporous-rich
nitrogen-doped carbon was synthesized by carbonizing the uni-
formly anchored ZIF-8 particles on the graphene oxide sheet (ZIF-
8@GO), while the mesopore formation was obtained by the
nonflammable gaseous byproduct released under thermal decom-
position of melamine. High specific capacities of 775 (at 1100 cy-
cles) and 650 mAh g
1 (at 1000 cycles) were obtained at high
current densities of 1000 and 2000 mA g
1, respectively, for the
melamine-modified carbon material. Superior rate performance,
high specific capacity, and long-term cycle stability of melamine-
modified sample were attributed to the synergistic contribution
from hierarchical mesoporous structure and electrical conductivity
from graphene and nitrogen-doped carbon facilitating ion trans-
port and electrolyte percolation resulting in the activation process
during charge/discharge cycles.
2. Experimental section
2.1. Materials and synthesis
Synthesis of ZIF-8: ZIF-8 crystals were synthesized by mixing
0.366 g of Zn(NO3)2$6H2O (Sigma Aldrich, 98%) and 0.811 g of 2-
methylimidazole (Sigma Aldrich, 99%) dissolved in 12 mL and
20 mL of methanol, respectively. The mixed solution was stirred for
3 h and the final solid was collected by centrifuging at 8000 rpm for
3 min, followed by washing with methanol for three times. The
collected sample was dried at 50  C overnight for further
characterization.
Synthesis of ZIF-8@GO: Graphene oxide (GO) was purchased
from the Standard graphene company, South Korea. ZIF-8@GO was
291
prepared following the reported procedure [18]. Typically, 0.366 g
of Zn(NO3)2$6H2O and 0.811 g of 2-methylimidazole were dissolved
in 12 mL and 20 mL of methanol, respectively. Then, the solutions of
Zn(NO3)2 and 2-methylimidazole were mixed to get a clear solution
of ZIF-8. Subsequently, 8 mL of GO solution (1 mg mL
1, in water/
methanol mixture with 1:4, v/v) was immediately added to the ZIF-
8 solution. After stirring for 3 h, the grey precipitate was collected
by centrifuging at 8000 rpm for 3 min and washed with methanol
three times. After drying at 50  C for 12 h, ZIF-8@GO was obtained.
The amount of GO with respect to the Zn(NO3)2 was maintained at
2 wt%.
Synthesis of mesoporous-rich nitrogen-doped carbon@-
graphene (MPNC@G) sheet: Firstly, a certain amount of ZIF-8@GO
was dispersed in 50 mL of methanol by sonication for 20 min, fol-
lowed by the addition of desired amount of melamine. The mixture
was then stirred in a water bath maintained at 80  C, to remove
methanol completely. Subsequently, the obtained powder was
subjected to two-step calcination procedure, namely 800  C/3 h
and 950  C/1 h under Ar atmosphere for the carbonization and
removal of Zn metal from ZIF-8. A low temperature firing step
(<500  C) which is typically employed for obtaining nitrogen
doping in the carbon materials using melamine precursor iastabi-
lization of nitrogen in the framework was intentionally avoided.
The unmodified sample was also synthesized without melamine
following same calcination steps. The as-obtained unmodified and
melamine-modified ZIF-8@GO samples after calcination were
denoted as porous nitrogen-doped carbon@graphene (PNC@G)
sheets and MPNC@G sheets, respectively. The contents of melamine
were varied to optimize the mesoporous structure, and ratio of
weight percentage of melamine to ZIF-8@GO was fixed at 50%:50%
and 66%:34%, denoted as MPNC@G-1 and MPNC@G-2, respectively.
Synthesis of reference materials: Reference samples were
synthesized for understanding the role of melamine on the indi-
vidual precursors (ZIF-8 and graphene) and evaluating the elec-
trochemical property of MPNC@G samples (carbonized product of
ZIF-8 þ melamine þ graphene). The reference sample containing
only ZIF-8 and melamine were made to evaluate the effect of
melamine on ZIF-8 and was denoted as porous nitrogen-doped
carbon (PNC; carbonized product of ZIF-8 þ melamine). The other
reference sample, containing only graphene and melamine were
made to evaluate the effect of melamine on graphene sheet, was
denoted as porous nitrogen-doped graphene (PNG; carbonized
product of graphene þ melamine). The PNC sample was prepared
by simple mixing of ZIF-8 with melamine following the same
calcination temperature employed for MPNC@G sample. The PNG
sample was prepared by simple mixing of GO with melamine and
calcining at same temperature. The carbonization of ZIF-8 only was
also carried out at the same temperature to form nitrogen-doped
porous carbon and was denoted as PC (carbonized product of ZIF-
8).
2.2. Electrochemical measurements
The electrochemical measurements were performed using a
coin cell assembly (CR 2032), which was assembled in an argon-
filled glove box with lithium metal as the counter electrode. The
working electrode was fabricated with 80 wt% active material,
10 wt% acetylene black, and 10 wt% polyvinylidene fluoride binder
on a copper foil collector with an active material loading of
~1 mg cm
2. The electrolyte was 1 M LiPF6 dissolved in a mixture of
ECeDEC (1:1 vol ratio) solution. The electrochemical impedance
spectra and cyclic voltammogram (CV) of the electrodes were
measured using the Autolab electrochemical workstation and a
scan rate of 1 mV s
1 was used in the latter. The chargeedischarge
measurements were collected using a Nagano BTS-2004H battery
292 S. Gayathri et al. / Electrochimica Acta 318 (2019) 290e301
test system in the potential range of 0.01 and 3.0 V.
2.3. Materials characterization
X-ray diffraction (XRD) was performed using Rigaku D/Max
2400 with Cu Ka radiation at a scan rate of 2 min
1 in the range
10  2q  80 . Field emission-scanning electron microscopy (FE-
SEM) and high-resolution transmission electron microscopy (HR-
TEM) were performed using a Hitachi S-4800 and FEI Tecnai F20
(200 kV), respectively, at the Korea Basic Science Institute (KBSI),
Gwangju, South Korea for analyzing the nanostructure of the
samples. The BrunauereEmmetteTeller (BET) specific surface area
was determined by nitrogen adsorptionedesorption at 77 K on a
Belsorp mini analyzer. Laser Raman spectra were collected by using
a Horiba Jobin Hyon ARAMIS using a backscattering geometry in
the Korea Basic Science Institute (KBSI), Gwangju center, South
Korea. X-ray photoelectron spectra (XPS) measurement was per-
formed with VG Multilab 2000 instruments using Al as target
anode for X-ray generation. The X-ray photon energy (Al Ka) was
1480 eV with a line width of 0.5 eV. The CHNS elemental analysis
measurement was carried out using Vario Max CN elemental
analyzer.
3. Results and discussions
The synthesis strategy for the MPNC@G nanosheets derived
from ZIF-8@GO and melamine is illustrated in Fig. 1. ZIF-8 is a metal
organic framework made of zinc ions coordinated to four imida-
zolate rings forming large porous structures and cavities which are
exploited in wide variety of applications including gas storage,
catalysis, drug delivery, sensing, and electronic devices. Typically,
the ZIF-8@GO precursor was synthesized by anchoring the ZIF-8
nanocrystals onto the layer of GO through the oxygen functional
groups of the latter [18]. Owing to the strong binding interaction
Fig. 1. Graphical representation of synthesis procedure of mesoporous-rich nitrogen-
doped carbon anchored graphene sheets (MPNC@G) using melamine.
between the Zn ions of the ZIF-8 framework and oxygen groups of
GO, the ZIF-8 nanocrystals are anchored and homogeneously
distributed on both sides of GO sheets. The anchored ZIF-8 nano-
particles in GO act as a spacer and prevent the agglomeration of
individual graphene sheets during high-temperature carboniza-
tion. Melamine molecule was employed for obtaining mesoporous
structure through pore expansion in the final material during high-
temperature carbonization. Generally, melamine-derived N-doped
porous carbon has been reported with a nitrogen-stabilizing step to
retain large nitrogen content in the carbon sample through a low
temperature (250e400  C) annealing of melamine [19]. However,
in the current work, retaining the nitrogen content via nitrogen-
stabilizing step was not our interest, instead we exploit the antic-
ipated gaseous product evolved during high-temperature calcina-
tion of melamine for the pore generation and expansion in the ZIF-
derived carbon matrix and defect formation/binding site in the
graphene sheets. The evolution of gaseous byproduct from the
thermal decomposition of melamine is anticipated to increase the
mesopore structure in the final carbonaceous material [19]. During
carbonization, ZIF-8 is expected to form a graphene-like nano-
sheets, covering the preexisting graphene layers (obtained from
GO), while melamine altering the surface chemistry of these carbon
matrices. The carbonization of Zn-containing ZIFs (ZIF-7 and ZIF-8)
framework with the organic additive has been reported to form
graphene-like structures, attributed to the pre-melting and
decomposition of additive before the ZIF was completely carbon-
ized [20]. The expected MPNC@G nanosheets with high porosity,
nitrogen content, and sandwich structure would boost the elec-
trochemical performance of this anode material for lithium-ion
battery (LIBs).
The X-ray diffraction (XRD) pattern of ZIF-8 and ZIF-8@GO
samples before carbonization can be indexed with the crystalline
phase of ZIF-8 synthesized at room temperature as shown in Fig. 2a.
No significant difference was observed between the ZIF-8 and ZIF-
8@GO samples owing to the overlapping of the dominant peak of
ZIF-8 (112) plane with the expected GO (001) peak at the Bragg's
angle of ~12.5 . The XRD patterns of the carbonized samples
Fig. 2. (a) XRD patterns of ZIF-8, ZIF-8@GO, unmodified PNC@G, melamine-modified
MPNC@G-1, and MPNC@G-2 samples, and (b) Raman spectra of graphene oxide,
PNC@G, MPNC@G-1 and MPNC@G-2 samples depicting D-band and G-band, and (c)
FT-IR spectra of PNC@G, MPNC@G-1, and MPNC@G-2 samples.
 S. Gayathri et al. / Electrochimica Acta 318 (2019) 290e301
namely unmodified PNC@G and melamine-modified samples, viz.,
MPNC@G-1 and MPNC@G-2, changed significantly from ZIF-8@GO,
with main peak appearing at ~26 , assigned to the (002) plane of
graphitic carbon. The broad low-intensity peak imply that the
samples have a low degree of graphitization, which is consistent
with other carbon-based materials [21,22]. It should be noted that
the diffraction peaks of Zn metal or ZnO are absent in all the
carbonized samples, suggesting that the Zn metal could have
vaporized during high-temperature carbonization at 950  C. The
Raman spectra of the PNC@G, MPNC@G-1, and MPNC@G-2 nano-
structures disclose two characteristic peaks at 1352 and 1590 cm
1,
which are attributed to the D and G bands of the graphitic structure,
respectively as shown in Fig. 2b. The D band arises from the A1g
vibration mode of carbon with defects and disordering in sp2 hy-
bridized carbon lattice. The G band results from the highly ordered
crystalline carbon representing E2g vibration modes of CeC
stretching bonds. The chemical modifications occurred during the
high temperature carbonization process with melamine were
evaluated from the ID/IG value. The ID/IG ratios of the melamine-
modified mesoporous-rich samples, namely, MPNC@G-1 (ID/
IG ¼ 1.11) and MPNC@G-2 (ID/IG ¼ 1.16), is slightly higher than that
of the unmodified PNC@G (ID/IG ¼ 1.09) and GO (ID/IG ¼ 0.95),
reflecting the formation of relatively defect-rich and disordered
structure in the graphene/carbon matrix, during carbonization with
melamine. The chemical composition and presence of the func-
tional group on the as-obtained carbon material were characterized
by Fourier transform-infrared spectra, as shown in Fig. 2c. The
PNC@G and modified MPNC@G samples show broad band at
3300 cm
1 corresponding to the presence of the NeH functional
group, which may in the form of pyridinic and pyrrolic type of ni-
trogen, which are generally formed in nitrogen-doped carbon
material [23]. The band at 1645 cm
1 suggests the presence of ni-
trogen in the form of C]N (pyridinic nitrogen), further confirming
the existence of nitrogen-containing functional group in this
nitrogen-doped carbon material. The bands at 1550 and 1230 cm
1,
are attributed to the C]C of aromatic ring and CeN of amine group,
respectively. Further, the carbon-based functional group, namely,
the CeH bands at 2920 and 2850 cm
1, were observed only in the
melamine-modified sample, which indicates the strengthening of
the CeH bonds during carbonization in presence of melamine
arising from graphitic carbon, and pyrrolic and defective pyridinic
nitrogen-containing rings.
The morphology and nanostructure of the as-prepared samples
were analyzed by scanning electron microscopy (SEM) and trans-
mission electron microscopy (TEM) and are shown in Fig. 3. The PC
sample (prepared by calcining ZIF-8 only) exhibited polyhedron-
shaped nitrogen-doped porous carbon with uniform size of
~50 nm and severe agglomeration (Figs. S1 and S2, Supporting in-
formation). The size and morphology of the PC sample was retained
even after calcining the ZIF-8 nanocrystals at high temperature. The
carbonization of ZIF-8 with melamine (PNC) retained the poly-
hedron morphology without any change (Fig. 3aed). Interestingly,
the PNC@G sample preserves the sheet-like morphology of gra-
phene sheets, in which the polyhedral-shaped PC (the carbonized
product of ZIF-8) is anchored and uniformly distributed onto the
surface of graphene sheets, significantly suppressing the agglom-
eration of polyhedral nanoparticles (Fig. 3eeh). With the use of
melamine, a drastic change in the morphology of the graphene
sheets and polyhedral particles was evident. The MPNC@G-1
sample exhibited tiny hollow structure with surface roughness on
the graphene sheets indicating the influence of melamine on the
structural modification of the sample (Fig. 3iel). It was apparent
that the polyhedral particles on the graphene sheets vanished
completely, suggesting complete decomposition of ZIF-8 polyhedra
in the presence of melamine. Extremely thin graphene sheets were
293
apparent in the melamine-containing MPNC@G-1 sample with
pore features, compared to pristine PNC@G. This may be attributed
to the conversion of anchored ZIF-8 polyhedral particles into
graphene-like structures on the preexisting graphene sheets via
pre-melting and decomposition of melamine (at ~350  C), before
the complete carbonization of ZIF-8 [24]. It is also likely possible for
the thinning of preexisting graphene sheets by the gas-assisted
exfoliation process [25,26], through the gases released from the
thermal decomposition of melamine at 950  C, which can also lead
to expansion of pores and new pore formation. With further in-
crease in the melamine content, shrinkage of preexisting graphene
and ZIF-8-derived graphene-like structures were evidenced,
forming further large pores in the MPNC@G-2, as shown in Fig. 3
mep. Therefore, the melamine-modified samples exhibited a
nanoporous graphene-like thin layer anchored uniformly on either
side of the graphene sheets. The changes in the morphology,
nanostructure, and surface chemistry of MPNC@G samples were
attributed to the melamine-induced effects, namely e the influence
of thermally decomposed gaseous byproducts of melamine and
favoring the complete decomposition of the ZIF-8 polyhedra in
presence of melamine.
The composition and crystallinity of the PNC@G and MPNC@G
nanostructures were further analyzed by TEM elemental mapping
and selected area electron diffraction (SAED), as shown in Fig. 4. As
observed, the nitrogen and oxygen elements are homogeneously
distributed on the carbon matrix of the PNC@G and MPNC@G
samples, suggesting that the ZIF-8-derived PNC polyhedral parti-
cles are dispersed uniformly on the graphene sheets forming a
sandwich-like nanostructure. In addition, owing to the evaporation
of Zn during the high-temperature carbonization process, Zn ele-
ments were hardly observed. The SAED pattern (Fig. 4e, 4j, and 4o)
reveals high crystalline nature of melamine-modified carbona-
ceous material (MPNC@G) compared to the unmodified PNC@G,
suggesting that the melamine improved the localized crystallinity
by increasing the degree of graphitization and favoring complete
decomposition of ZIF-8 during high-temperature carbonization.
The lithium storage properties of the nitrogen-doped carbona-
ceous anode material are highly dependent on the doped nitrogen
d dopant type and its content. Therefore, X-ray photoelectron
spectroscopy (XPS) measurements were performed to identify the
type of nitrogen and quantify its contents in these samples, as
shown in Fig. 5. The atomic percentage of nitrogen present in the
synthesized carbonaceous samples were estimated from the CHNS
elemental analysis and their values are 14.8%, 11.9%, and 12.2%, for
pristine PNC@G, and melamine-modified MPNC@G-1, and
MPNC@G-2 samples, respectively (Table 1). The retention of ni-
trogen in the pristine PNC@G sample derived from the nitrogen-
rich ZIF-8 upon carbonization, corroborates with the earlier
report [20]. As melamine is commonly used as a source of nitrogen
doping for carbon matrix, it is expected that the melamine-
modified samples show an increased nitrogen content. However,
the apparent decrease in the nitrogen contents (11.9% and 12.2%) in
the melamine-modified samples, is attributed to two possible
reasons. (a) the non-utilization of nitrogen-containing gases for
doping via an intentional high temperature carbonization (950  C),
precluding the nitrogen stabilization firing step at low temperature.
It is to be noted that, nitrogen-doping in carbon using melamine
precursor is generally performed by stabilizing nitrogen through a
low temperature firing step at 250  C before the carbonization step
[19], (b) stimulating the removal of pre-existing nitrogen from the
carbon matrix derived from ZIF-8, by the nonflammable gases (N2)
evolved during thermal decomposition of melamine [27]. More-
over, though melamine contains 67% of nitrogen by mass, all the
nitrogen contents were released as a gas at high temperature
(950  C) leaving a porous structure, rather than influencing
294 S. Gayathri et al. / Electrochimica Acta 318 (2019) 290e301
Fig. 3. FE-SEM images of (a, b) PNC, (e, f) PNC@G, (i, j) MPNC@G-1, and (m, n) MPNC@G-2 and HR-TEM images of (c, d) PNC, (g, h) PNC@G, (k, l) MPNC@G-1, and (o, p) MPNC@G-2.
nitrogen doping into the carbon material which are usually pre-
pared at lower temperature (<700  C) [22]. Therefore, controlling
the porous structure using melamine was the scope of this study
rather than altering the nitrogen content. Interestingly, the loss of
nitrogen atoms from the carbon matrix, during high temperature
carbonization, immensely improves the degree of crystallization of
the final carbon material, as evidenced from the SAED pattern
(Fig. 4e, 4j, 4o).
The high-resolution XPS N1s spectrum of the as-synthesized
sample is shown in Fig. 5a, which can be deconvoluted into three
components, depicting three types of nitrogen, namely, pyridinic
nitrogen (NPy, 398.5 ± 0.2 eV), pyrrolic nitrogen (NPr,
399.5 ± 0.2 eV), and graphitic nitrogen (NG, 400.3 ± 0.3 eV),
respectively. Nitrogen doping in the carbon material is known to
improve their electronic conductivity, arising from delocalized
conjugation of the lone electron pairs of nitrogen atom with the
sp2-hybridized carbon framework, offering more active sites and
enhanced charge transfer, desirable for the Li-ion battery perfor-
mance [24,28]. The XPS result indicates that the content of graphitic
nitrogen (located within graphene sheets) has increased enor-
mously for the melamine-modified MPNC@G sample compared to
unmodified PNC@G (Table 2). It should be noted that the graphitic
nitrogen and pyridinic nitrogen contributes to the electronic
conductivity due to their sp2 hybridization, which might improve
the electrochemical performance of nitrogen-doped carbon.
Therefore, it is reasonable to envisage an enhanced battery per-
formance for the melamine-modified sample with higher graphitic
nitrogen in the carbon matrix. The presence of lower pyrrolic ni-
trogen (NPr) fraction in the melamine-modified sample is advan-
tageous for the battery performance due to the reduced non-
conducting sp3 hybridized regions. This differential nitrogen con-
tents with the inclusion of melamine may be attributed to the non-
stabilization of nitrogen during calcination leading to higher
graphitic nitrogen contents in MPNC@G than the unmodified
PNC@G [19,28]. A peak shift to the lower binding energy for the
graphitic and pyrrolic nitrogen's is prominent in the melamine-
modified samples compared to PNC@G. The weakening of chemi-
cal interaction between C- and N- atoms in the nitrogen-doped
graphene samples is attributed to the presence of stronger neigh-
boring CeH bonds as observed from FT-IR results of melamine-
modified sample (Fig. 2c). However, the unaltered binding en-
ergies of pyridinic nitrogen can be ascribed to the partial conver-
sion of pyridinic nitrogen to the graphitic nitrogen as reported in
the literature [29], which also corroborates with our results of in-
crease in the fraction of graphitic nitrogen of melamine-modified
samples (Table 2). The C 1s spectrum of the melamine-modified
 S. Gayathri et al. / Electrochimica Acta 318 (2019) 290e301 295

Fig. 4. HR-TEM elemental mapping of (aed) PNC@G, (fei) MPNC@G-1, and (ken) MPNC@G-2 depicting the N1s, C1s, and O1s, and TEM selected area electron diffraction of (e)
PNC@G, (j) MPNC@G-1, and (o) MPNC@G-2.

MPNC@G samples exhibited different kinds of carbon indicated by
multiple deconvoluted peaks at 284.5 eV (carbon in the graphene
ring), 286.2 eV (C]N), and 288.4 eV (NeC]O) (Fig. S3, Supporting
information).
The effect of melamine on the surface area, pore size distribu-
tion, and pore volume of the samples was studied using nitrogen
adsorptionedesorption isotherms (Fig. 6). In the unmodified
PNC@G sample, the nitrogen adsorption occurs at a relatively low
pressure indicating the presence of a micropore-filling effect. The
significant nitrogen adsorption with a relatively middle pressure
suggests capillary condensation of nitrogen in the mesopore
(2e50 nm) or macropore (50e100 nm) structures. Therefore, the
unmodified samples are found to possess more micropores
(2 nm), than the meso/macropores. The adsorption/desorption
isotherms of the melamine-modified sample exhibit similar shapes,
except a small nitrogen adsorption at low pressure indicating the
presence of a large content of mesopores (Fig. 6a). The specific
BrunauereEmmetteTeller (BET) surface area of the unmodified
PNC@G sample shows a higher value of 480 m2 g
1. After carbon-
ization with melamine, the specific surface areas are reduced to 362
296 S. Gayathri et al. / Electrochimica Acta 318 (2019) 290e301

Fig. 5. XPS N 1s spectra of unmodified PNC@G, MPNC@G-1, and MPNC@G-2 samples

deconvoluted into three components, namely pyridinic N (N-6, 398.1 eV), pyrrolic N
(N-5, 399.5 eV), and graphitic N (N-Q, 401 eV).

Table 1
Elemental analysis of carbon and nitrogen contents from CHNS.

Material Element Content (%)

PNC@G Carbon 85.2 Fig. 6. (a) Nitrogen adsorption-desorption BET isotherms where Abs. and Des. are
Nitrogen 14.8 denoted for adsorption and desorption, respectively, (b) Pore size distribution of
MPNC@G-1 Carbon 88.1 PNC@G, MPNC@G-1, and MPNC@G-2 samples in the whole range of 0e100 nm, and an
Nitrogen 11.9 inset of selected pore diameter ranging from 0 to 50 nm, and (c) Statistics of selected
MPNC@G-2 Carbon 87.8 region of cumulative pore size distributions in the pore diameter ranging from 0 to
Nitrogen 12.2 50 nm denoting micro- and mesoporous structures.

and 240 m2 g
1 for the MPNC@G-1 and MPNC@G-2 samples, MPNC@G-2 arise from the higher macropore content [30]. The
respectively (Table 3). The pore size distribution suggests the macropore formation in the MPNC@G-2 sample is ascribed to the
presence of a larger mesopore contribution (predominantly expansion of pores by the copious amount of gaseous product,
2e30 nm) when melamine was used during carbonization than along with partial destruction and reorganization of mesoporous
that of the unmodified PNC@G, as shown in Fig. 6b inset, which is network.
the reason for the low surface area of mesoporous-rich melamine- It should be noted that the carbonization of the organic mole-
modified samples [28]. The low melamine content sample cules in the 2-methylimidazole precursor leads to the formation of
(MPNC@G-1) exhibited the highest mesopore contribution. Further mixed micropore (large) and mesopore (small) structures in the
increase in the melamine content (MPNC@G-2) leads to the unmodified PNC@G sample [11]. However, the carbonization
decrease in the mesopores and marginal increase in the macro-
pores due to partial expansion of mesopores. The decrease in the
mesoporous structure, arise due to the destruction and reorgani- Table 3
zation of porous network due to excess evolution of gaseous BET parameters of surface area and pore volume of synthesized samples.
byproducts from melamine (Fig. 6c) as noted in the SEM and TEM
Material Surface area (m2 g
1) Pore volume (cm3 g
1)
results (Fig. 3mep). The low surface area of the melamine-modified
samples (MPNC@G-1 and MPNC@G-2) is the characteristic feature PNC@G 480 1.04
MPNC@G-1 362 0.98
of mesopore-rich samples, while a much smaller surface area of
MPNC@G-2 224 1.05

Table 2
Nitrogen contents estimated from X-ray photoelectron spectroscopy.

Samples Type of nitrogen content (%)

Pyridinic nitrogen (NPy) Pyrrolic nitrogen (NPr) Graphitic nitrogen (NG)

PNC@G 46.9 24.6 28.6
MPNC@G-1 43.5 18.0 38.5
MPNC@G-2 37.1 11.3 51.5
 S. Gayathri et al. / Electrochimica Acta 318 (2019) 290e301
process in the presence of melamine leads to the mesoporous
structure with interconnected pores by the structural reconstruc-
tion of the polyhedron-anchored carbon/graphene sheets at high
temperature as evidenced from SEM, TEM, and BET techniques.
Therefore, it is reasonable to conclude that the melamine is quin-
tessential in promoting the formation of mesoporous structure
which is beneficial for the electrochemical performance of Li-ion
battery. The above results demonstrate that the melamine-
modified MPNC@G sample possessing graphitic nitrogen and
mesoporous structure were successfully synthesized. The meso-
porous structure with interconnected pores offers a favorable
pathway for the fast percolation of electrolyte and transportation of
ions, along with more active sites for lithium-ion storage, and thus,
it may lead to improved specific capacity and enhanced rate
capability of the melamine-modified mesoporous-rich MPNC@G
material. Therefore, it is anticipated that the new kind of MPNC@G
nanostructure will boost the electrochemical performance of Li-ion
batteries owing to the presence of the mesoporous structure,
increased carbon content, nitrogen doping on the conducting gra-
phene sheets as platform, and high degree of graphitization.
The lithium storage properties of the melamine-modified
carbonaceous material were evaluated by various electrochemical
techniques. The cyclic voltammetry (CV) curves of the synthesized
samples were recorded between 0.01 and 3.0 V vs. Li/Liþ, as shown
in Fig. 7. Both the unmodified (PNC@G) and melamine-modified
(MPNC@G-1 and MPNC@G-2) samples display similar CV charac-
teristics of carbon-based anode materials (Fig. S4, Supporting
Fig. 7. (a) Cyclic voltammogram of MPNC@G-1 at a scan rate of 0.1 mV s
1 in the potential range of 0.01e3 V for three cycles, (b) Voltage profile of MPNC@G-1 at current density of
100 mA g
1 (C/5) for initial three cycles, (c) Cycling performance of the samples at current density of 100 mA g
1, and (d) Rate performance of the samples at different current
densities of 100, 200, 500, and 1000 mA g
1.
297
information). The first cathodic sweep exhibit two irreversible
peaks namely intense 0.71 and weak 1.16 V owing to the formation
of solideelectrolyte interphase (SEI) layer and the occurrence of
side reactions on the electrode surface, respectively, which disap-
pear in the subsequent cycles. In the second and third cycles,
anodic/cathodic curves almost overlapped, indicating excellent
reversibility of the PNC@G and MPNC@G electrodes which are
stable towards reversible Liþ intercalation.
The voltage profile and cycling performance of the melamine-
modified MPNC@G and unmodified PNC@G samples were
measured at low current density of 100 mA g
1 (1C ¼ 500 mA g
1),
with the potential window of 0.01e3.0 V vs. Liþ/Li. Both the samples
show similar voltage profiles, which are the characteristic features
of carbonaceous material (Fig. 7b and Fig. S5, Supporting infor-
mation). The first discharge capacity of the melamine-modified
MPNC@G samples is higher than that of the unmodified PNC@G
sample, as shown in Fig. 7b and c. The first discharge capacities of
the melamine-modified MPNC@G-1 and MPNC@G-2 samples are
~1900 and ~1500 mAh g
1, respectively, while that of the unmod-
ified PNC@G sample is ~1250 mAh g
1 at 100 mA g
1. A large irre-
versible capacity loss occurs in the second cycle, which is attributed
to the unavoidable decomposition of the electrolyte and formation
of the solid-electrolyte interphase (SEI) film. This observation is
consistent with the CV results (Fig. 7a), in which the cathodic peaks
disappear in the second and third cycles. The mesopore-rich
MPNC@G-1 sample exhibited a specific capacity of 700 mAh g
1
at the 30th cycle at 100 mA g
1, which is similar to the unmodified
298 S. Gayathri et al. / Electrochimica Acta 318 (2019) 290e301
sample, as shown in Fig. 7c. The excess melamine sample
(MPNC@G-2) shows the lowest cyclability after 30 cycles at
100 mA g
1. Further, the rate performance was tested from 100 to
1000 mA g
1 showing considerable difference between MPNC@G
and PNC@G anodes for LIBs as shown in Fig. 7d. The MPNC@G-1
sample delivers high reversible discharge capacities of ~730,
~613, ~524, and ~450 mAh g
1 at current densities of 100, 200, 500,
and 1000 mA g
1, respectively, which is higher than the PNC@G
sample. In addition, the capacities of MPNC@G-1 remained stable at
all current densities which restored after discharging at higher rate,
suggesting superior rate performance, good reversibility, and high
specific capacity, compared to PNC@G sample. The low initial ca-
pacities of high melamine containing sample (MPNC@G-2) at all
current densities arise due to the partial destruction of the con-
ducting carbon framework due to excess evolution of gaseous
product from melamine.
The cycling performance at high C rates and cycling stabilities
are largely determined by the mesoporous structure of the active
material which generally reduces the diffusion path of ions and
electrolyte, and electronic conductivity which arise from the con-
ducting graphitic carbon, graphitic nitrogen network, and nitrogen
doping. The cycling performance at high current densities, namely
1000, 2000, and 5000 mA g
1, were measured by activating the
electrodes at lower current density of 100 mA g
1 for the three
cycles as shown in Fig. 8a. The specific discharge capacity of
melamine-modified MPNC@G-1 at 1000 mA g
1 (2C) after the
activation cycle was ~460 mAh g
1, while those of the unmodified
PNC@G and MPNC@G-2 electrodes were 440 mAh g
1 and 370 mAh
g
1, respectively. The drastic increase in the specific capacity with
cycling for the MPNC@G-1 electrode was apparent, reaching
775 mAh g
1 after 1100 cycles which is 150% of its initial capacity
and close to double the capacity of unmodified electrode. The in-
crease in the specific capacity with cycling of MPNC@G-1 electrode
may be attributed to the activation of mesoporous-rich structure.
The presence of abundant mesopores in the melamine-modified
electrode is beneficial for the percolation of the electrolyte and
Li-ion diffusion through the porous structure, leading to an increase
in the cycling stability during chargeedischarge process [31e33].
Fig. 8. (a) Cycling performance of the samples at current density of 1000 mA g
1 (2C),
after initial activation at 100 mA g
1 for three cycles, and its (b) capacity retention at
the 800 cycle.
The capacity of unmodified PNC@G electrode after intial decrease,
has retained ~400 mAh g
1 after 800 cycles, which was unable to
endure the high current load on further cycles. Despite a low initial
capacity of MPNC@G-2 electrode, an increase in the discharge ca-
pacity retained till 1100 cycles and crossing the unmodified PNC@G
electrode at above 550 cycles. Therefore, in addition to high specific
capacity and superior rate performance, the MPNC@G-1 demon-
strated high cycling stability at high current densities due to their
mesoporous structure which facilitate the ionic/electrolyte diffu-
sion during cycling, enhanced electronic conductivity, and high
degree of graphitization.
The MPNC@G samples are basically made of multicomponent
mixture of ZIF-8, graphene, along with melamine as the modifier,
hence its vital to explore the individual effects of each component
on the electrochemical performance for a deeper insight into the
underlying mechanism. Therefore, reference samples, namely, PNC
(the carbonized product of ZIF-8 and melamine only) and PNG (the
carbonized product of GO and melamine only), were synthesized
and their electrochemical performance were investigated at same
current density of 1000 mA g
1 with initial activation for three
cycles at 100 mA g
1. Interestingly, the PNC electrode exhibited a
high specific capacity of 480 mAh g
1 of the fourth cycle (after three
activation cycle) than the melamine-modified MPNC@G-1
(460 mAh g
1). However, the PNC electrode exhibited poor cycling
stability with capacity retention of only 53% after 1000 cycles
which is the lowest among all the samples while MPNC@G-1 show
150% capacity retention. In the case of PNG electrode, a low initial
specific capacity of 360 mAh g
1 was obtained but exhibit a high
capacity retention of ~105% indicating the occurrence of activation
process from the graphene sheets. Similarly, PNC electrodes
exhibited high specific capacities than the MPNC@G and PNC@G
samples at all the current densities except the first cycle, while PNG
electrode exhibited the lowest specific capacities among the sam-
ples (Fig. S6, Supporting information). The trend in the capacity
retention after 800 cycles were compared and found to be in the
order MPNC@G-1 > MPNC@G-2 > PNG > PNC@G > PNC with values
of 163%, 120%, 110%, 91%, and 68%, respectively. The first three
sample containing graphene þ melamine alone shows the activa-
tion process with capacity retention over 100%. While the last two
samples, PNC@G containing ZIF-8 and graphene and the PNC
sample containing only ZIF-8 and melamine, showing no electro-
chemical activation characteristics (Fig. 8b). These results clearly
demonstrated that high specific capacity stems from the ZIF-8-
derived carbon material owing to enhanced electronic conductiv-
ity from nitrogen-doping, high degree of graphitization, and mes-
opore formation which were all induced by the melamine molecule
during carbonization step. The activation process and long-term
stability of the electrode arise from the graphene sheets via the
melamine-induced surface-modification forming a mesoporous-
rich structure e facilitating an efficient ionic and electrolyte
transport and providing active binding sites through the defective
surfaces of graphene. It is to be noted that the nitrogen doping in
graphene sheet may be unrealistic due to possible release of ther-
mally unstable nitrogen gas during high temperature carbonization
from melamine (containing 67 wt% of nitrogen) for the mesopore
formation. Therefore, the superior electrochemical performance of
the MPNC@G-1 namely high discharge capacity and long cycle
stability arise from the synergistic effect from high electronic
conductivity of melamine-modified ZIF-derived carbon and
mesoporous-rich graphene sheets, respectively.
The initial coulombic efficiencies of the melamine-modified
MPNC@G-1 (36%) and MPNC@G-2 (27%) electrodes are relatively
lower than that of the unmodified PNC@G (47%). This low
coulombic efficiency arises from the mesoporous-rich MPNC@G
electrodes forming intense irreversible solid electrolyte interface
 S. Gayathri et al. / Electrochimica Acta 318 (2019) 290e301
through the large contact area between mesoporous-rich electrode
and electrolyte. However, the coulombic efficiencies of all the
electrodes recovered to ~99%, soon after the first cycle and main-
tained the same with cycling. The MPNC@G-1 electrode shows
excellent electrode performance for LIBs at high current densities
namely, 2000 mA g
1 and 5000 mA g
1 with initial activation cy-
cles (three cycles at 100 mA g
1) as shown in Fig. 9. The MPNC@G-1
electrode retained capacity of 660 mAh g
1 at 2000 mA g
1 (4C)
after 1000 cycles with the capacity retention of 127%. While the
PNC@G electrode retained 340 mAh g
1 over 500 cycles with ca-
pacity retention of 75%. In addition, a high specific capacity of
390 mAh g
1 was obtained over 2000 cycles at 5000 mA g
1 (10C)
with capacity retention of 91%. The melamine-modified MPNC@G-
1 electrode demonstrates superior electrochemical performance
for LIBs compared to other carbon anode material including
nitrogen-doped porous carbon derived from ZIFs. These results
demonstrate that the MPNC@G-1 sample could be a promising
anode material for the high energy density Li-ion battery owing to
the synergistic effect of the melamine-induced properties viz. high
electronic conductivity of ZIF-derived nitrogen-doped carbon, and
dominant mesoporous-rich structure on the melamine-modified
graphene sheets facilitating efficient ionic and electrolyte
transport.
The activation process describing the increase in the specific
capacity with cycling in porous carbon-based electrodes has been
reported earlier involving peanut-shell-derived hard carbon [34],
mushroom-derived porous carbon [35], hush-derived carbon [36],
and other carbon material [11,37]. However, their mechanism was
still not clearly understood and different views were reported but
were generally assigned to the activation process during cycling
[37]. Few of the reported activation mechanisms described through
(a) favoring the accessibility of unexposed mesopore upon cycling
[35], (b) insertion/extraction of lithium might make porous struc-
ture collapse, leading to decrease in the volume strain energy [34],
and (c) opening some channels and gaps, where charge and lithium
ions could move freely, through the broken wall of porous carbon
resulting from cycling and subsequently e increasing the capacity
[36]. We believe that the probable mechanism of activation process
in the current work may involve, a gradual opening of the channels
Fig. 9. Cycling performance of the samples at current density of (a) 2000 mA g
1 (4C)
and (b) 5000 mA g
1 (10C) after initial activation at 100 mA g
1 for three cycles each.
299
and gaps by volume expansion and capillary action inside the pores
during cycling, where an increase in the electrolyte diffusion and
ion transport could improve the discharge capacity and cycle
stability.
The high specific capacity, superior rate performance, and cycle
stability of the melamine-modified MPNC@G electrode can be
attributed to its exceptional mesoporous structure, high electronic
conductivity, and high degree of graphitization created by the
melamine-induced high temperature carbonization of ZIF and GO
precursor. Typically, during carbonization, ZIF nanoparticles in
presence of melamine are converted to functional nitrogen-doped
carbon with micro/mesoporous structure, high specific surface
area, and promoted degree of graphitization. The graphene sheets
basically serve as a structure-directing agent and potential platform
for nucleation, growth, and stabilization of ZIF-8 nanocrystals.
However, graphene sheets under high temperature carbonization
with melamine, forms distinct mesoporous network, and defective
sites in the surface providing active binding sites for Li-ion storage.
This unique nanostructure containing both nitrogen-doped carbon
nanoparticles and graphene sheets not only serves as a channel for
fast electron transport but also enhances the electrolyte percolation
and functions as a reservoir for Li storage through the mesoporous
structure [7]. More importantly, the melamine generates meso-
pores and acts as a pore-expander owing to the evolution of the
nitrogen gas during the high-temperature carbonization process. In
addition, the pores can help in buffering volume variation during
charge/discharge cycles and maintain mechanical integrity of
anode, allowing the accessibility of the electrolyte and fast trans-
port of Liþ, steering to a high discharge capacity and enhanced
cycling performance [38]. Therefore, the role of melamine in the
improved lithium storage performance was elucidated, revealing
that melamine acts as a porogen and pore expander in ZIF and GO
facilitating a rapid ionic and electrolyte diffusion and increasing the
total carbon content due to the loss of heteroatoms at high tem-
perature leads to high electronic conductivity.
To investigate the electrochemical kinetics occurring at the
electrode/electrolyte interfaces and the Li-ion transport within the
battery cell, electrochemical impedance spectroscopy (EIS) was
performed before and after cycling at 1000 mA g
1 as shown in
Fig. 10. The Nyquist plot of MPNC@G-1 shows lower charge transfer
resistance of 21 U compared to that of unmodified PNC@G (26 U)
and MPNC@G-2 (30 U) electrodes which agree well with their
cycling performance (Figs. 8 and 9). The charge transfer resistance
of the reference samples - PNC and PNG electrodes are 35 and 41 U,
respectively, which is slightly higher than other samples (Fig. S7,
Supporting information), and corroborates with the lower
discharge capacity in the first cycle (Fig. 8a). After cycling, the
melamine-modified samples show decreased resistance, which
further evidences the activation processes. This suggests that the
melamine-modified MPNC@G-1 electrode promotes the electronic
and ionic conductivity, enhancing the electrochemical performance
of the developed electrodes. Therefore, the synergistic effect of the
melamine-induced properties of ZIF@GO namely high electronic
conductivity and high degree of graphitization of ZIF-8 derived
nitrogen-doped porous carbon, and mesoporous-rich structure
from the graphene layers with active binding sites for Li storage,
enhances the specific discharge capacity and long cycle stability,
respectively, leading to enhanced electrochemical performance of
the developed anode material for the Li-ion batteries.
4. Conclusion
A mesoporous-rich MPNC@G electrode was synthesized
through the carbonization of ZIF-8 anchored GO sheets in the
presence of melamine as a porogen at high temperature. Unlike the
300 S. Gayathri et al. / Electrochimica Acta 318 (2019) 290e301
Fig. 10. Electrochemical impedance spectra of the synthesized samples (a) before cycling and (b) after 800 cycles at current density of 1000 mA g
1.
unmodified PNC@G, the MPNC@G electrode shows mesoporous-
rich structure which discloses that melamine apart from being
pore-directing agent in graphene, also acts as pore expander in
nitrogen-doped porous carbon. The presence of melamine also
improved the degree of graphitization and electronic conductivity
of the nitrogen-doped carbon, in addition to mesoporous structure
and active binding sites in the graphene layers. The mesoporous
structure facilitated efficient electrolyte percolation and ion
transport, leading to an enhanced electrochemical performance of
the electrode in Li-ion battery. The MPNC@G-1 anode material
retained high specific capacity of ~775 mAh g
1 after 1100 cycles, at
1000 mA g
1 with capacity retention of 150% revealing the activa-
tion process through the mesoporous network. The outstanding
electrochemical performance of the MPNC@G-1 namely, excellent
long-term cycle stability, rate performance, and high specific ca-
pacity can be attributed to the synergistic effect of mesoporous
structure in the graphene facilitating ion/electrolyte transport, and
electronic conductivity in the nitrogen doped porous carbon ma-
terial, respectively. Thus, the melamine-modified nitrogen-doped
carbonaceous material has demonstrated to be a promising alter-
native to the commercial graphite anode for high-performance Li-
ion batteries.
Acknowledgement
This work was supported by the Priority Research Centers Pro-
gram through the National Research Foundation of Korea (NRF)
funded by the Ministry of Education, Science, and Technology
(2018R1A6A1A03024334) and the Nano Material Technology
Development Program through the National Research Foundation
of Korea (NRF) funded by the Ministry of Science, ICT, and Future
Planning (2017M3A7B4014045).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.electacta.2019.06.054.
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