Carbon 152 (2019) 24e32

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Synthesizing multilayer graphene from amorphous activated carbon

via ammonia-assisted hydrothermal method
Ping Liu a, Zhichun Si a, *, Wei Lv a, Xiaodong Wu b, Rui Ran b, Duan Weng a, b,
Feiyu Kang a, b
a
Graduate School at Shenzhen, Tsinghua University, Shenzhen City, 518055, China
b
The Key Laboratory of Advanced Materials of Ministry of Education, School of Materials Science and Engineering, Tsinghua University, Beijing City, 10084,
China

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

Article history: A facile way to synthesize multilayer nitrogen-doped graphene (NG) from amorphous activated carbon
Received 11 March 2019 (AC) without metal catalyst was successfully developed via ammonia-assisted hydrothermal method at
Received in revised form 200
C. The method's crucial advantage relied on harnessing unique ammonia hydrothermal mecha-
30 May 2019
nisms to change the amorphous carbon into multilayer graphene and provide an energy-save and metal-
Accepted 31 May 2019
Available online 1 June 2019
free approach. The NG products were consisted of 2e10 graphitic layers, which could form highly
conductive network for electrodes. The hydrothermal process could trigger the reduction of oxygenates
on the base unit (graphite nanocrystallites) of amorphous carbon by ammonia, leading to growth of basic
units to multi-layer graphene. Compared with the traditional preparation via high temperature and
pressure processing or catalytic graphitization by transition metals, the as-prepared multilayer graphene
via metal-free and “green” method in a relative mild condition represented a high surface area and pore
volume. The NG was used as electrode material of supercapacitors and showed high capacitance
retention.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction encapsulated catalysts that were difficult to remove. Therefore,

The preparation of synthetic graphite (or artificial graphite)
from amorphous carbons was first achieved by Edward Goodrich
Acheson via vaporizing the silicon from carborundum at high
temperature (> 4400 K) at the end of the nineteenth century [1]. It
was realized that only a few graphitizable carbons (GC), such as
coke and anthracite, can be thermally graphitized and most of other
amorphous carbons, such as carbon black, charcoal and coal, on the
contrary, were ‘non-graphitizable’ [2]. Various methods had been
developed to produce synthetic graphite from graphitizable carbon,
such as direct graphitization via high temperature and pressure
processing [3,4], catalytic graphitization by transition metals at
600e1000
C [5e7], electrochemical graphitization in molten salts
[8,9]. Obviously, the high temperature/pressure or electrochemical
process was energy intensive. The catalytic graphitization method
generally generated onion-like carbon with large amounts of
* Corresponding author.
E-mail address: si.zhichun@sz.tsinghua.edu.cn (Z. Si).
how to synthesize nano-graphite via metal-free method in mild
conditions is extremely attractive because of the huge application
requirements of high quality graphite.
Recently, graphene has attracted intensive interest due to its
extraordinary electronic, optical, thermal and mechanical proper-
ties. Graphene is a single sheet of graphite (a single layer of carbon
atoms bonded together in a hexagonal lattice), which was firstly
synthesized by chemical vapor deposition (CVD) and epitaxial
growth, such as the decomposition of ethylene on nickel surfaces
[10]. Xu et al. [11] reported a method of synthesizing large-area
high-quality graphene films on copper foil with a fast growth
rate. Another method for obtaining graphene was by simply tracing
a sample of bulk graphite across a substrate in a process known as
micromechanical cleavage [12]. Although these physical (or
physics-chemical) methods readily gave sheets of graphene that
can be used for fabricating various laboratory scale devices, it was
chemical exfoliation methods (by ultrasonic method or reduction
of graphene oxide) that presented the most likely opportunities for
large-scale graphene production [13e18]. However, chemical
exfoliation always led to impurity of graphene and graphene from

https://doi.org/10.1016/j.carbon.2019.05.082
0008-6223/© 2019 Elsevier Ltd. All rights reserved.
 P. Liu et al. / Carbon 152 (2019) 24e32
oxidation of graphite were always involved in the presence of
strong acids and oxidants. How to produce scalable graphene by
“more green approaches” is still a great challenge. Mohammad et al.
reported a hydrothermal method using ethanol and sodium as raw
materials, followed by pyrolysis to prepare multilayered and
disordered graphene in large scale [19]. Xing et al. synthesized
nitrogen-doped graphene as high performance anode materials for
lithium ion batteries via one-pot hydrothermal method using
hexamethylenetetramine as single carbon and nitrogen source and
MgO clusters as structural constructor [20]. However, using metal
as catalyst still can't be avoided in these reports. In this work, we
successfully presented an energy-save and metal-free method to
obtain well crystalized multilayer graphene (2e10 layers) from
activated carbon via ammonia-assisted hydrothermal route at
200
C without any further treatment.
Graphene and chemically modified graphene are promising
candidates as components in applications such as energy-storage
materials [21] and oxygen evolution catalysts [22]. The atomic
radius of nitrogen is comparable to that of carbon and contains five
valence electrons available to form strong covalent bonds. The
conjugation between the nitrogen lone-pair electrons and the
graphene p-system could modify the physical and chemical prop-
erties of graphene. The substitution of carbon atoms by nitrogen
ones influences the atomic charge distribution on the graphene
scaffold and creates “active sites” thus significantly increases the
electrochemical activity of nitrogen-doped graphene, known as N-
graphene (NG). In this concept article, graphene was obtained from
amorphous activated carbon via ammonia-assisted hydrothermal
method. The additional effect of this process was nitride modifi-
cation of graphene, which was beneficial to prepare high perfor-
mance energy-storage materials such as electrical double layer
(EDL) capacitors. Different from the previously reported results, the
multilayer graphene nanostructure in our case exhibited a high
Brunauer-Emmett-Teller (BET) surface area and pore volume. To
our knowledge, this is the first time for reporting such well-defined
multilayer graphene from amorphous activated carbon via a facile
ammonia-assisted hydrothermal method.
2. Experimental section
2.1. Chemicals
Asphalt coke powder was obtained from CNOOC (China National
Off-shore Oil Corp.). Potassium hydroxide (KOH, GR, 95%), sodium
hydroxide (NaOH, GR, 97%), Ammonia solution (AR, 25e28%) and
N-Methyl-2-pyrrolidone (NMP, AR, 98%), graphene nanosheet (GS)
were purchased from Aladdin (Shanghai). Other chemicals such as
acetylene black, polyvinylidene fluoride (PVDF, AR), and hydro-
chloric acid (HCl, AR, 36e38%), bought from Nanjing Chemical
Reagent CO. Ltd.. All solutions used were freshly prepared with
deionized water having a resistivity of 18.2 MU. All chemicals were
used as received without further purification.
2.2. Synthesis
In this work, an asphalt-derived activated carbon (AC) with
specific surface area of 2407 m2 g1 was prepared as the porous
carbon precursor via a chemical activation process. Specifically,
asphalt coke powder was heated on a corundum boat inserted
within a quartz tube furnace at 500
C for 2 h with Ar flow. Then the
carbonized samples (CSs) were mixed well with KOH (KOH:
CSs ¼ 3:1) and activated at 900
C for 1 h with Ar flow. The products
were washed by hydrochloric acid firstly and then washed by
distilled water until the pH of filtrate was about 7. Then, the
mixture was dried in a vacuum oven. After being ball milled, 0.5 g of
25
the obtained amorphous activated carbon was dispersed in 50 mL
aqueous ammonia. The suspension was transferred to a 100 mL
poly (tetrafluoroethylene) (Teflon)-lined autoclave, undergoing a
hydrothermal impregnation at 200
C for 10 h. After hydrothermal
impregnation, the mixture was washed by ethanol for several times
and dried to gain the NH3 hydrothermal (NG) sample. For com-
parison, 0.5 g of the amorphous carbon was dispersed in 50 mL
distilled water, undergoing the same hydrothermal impregnation
to gain non-NH3 hydrothermal AC (HTAC) sample. The similar hy-
drothermal experiments were done by totally or partly replacing
ammonia by NaOH while maintained the same pH value of solu-
tion, or lower down the ammonia concentration in the solution.
2.3. Characterizations
Transmission electron microscopy (TEM) investigations were
performed on a FEI Tecnai G2 microscope operated at 300 kV.
Atomic force microscopy (AFM) was examined on a MFP3D mi-
croscope. The AFM samples were prepared by dropping the NG
dispersion on the mica and characterized with a silicon cantilever
operating in tapping mode. Nitrogen sorption isotherm was
measured with a micromeritics BELSORP II (BEL JAPAN, Japan)
adsorption analyzer at 77 K. The pore size distribution (PSD) was
calculated based on density functional theory (DFT) method, using
nitrogen adsorption data and assuming a slit pore model. The
micropore volume (Vmic) was obtained using the t-plot (Hakins-
Jura equation) method. The total pore volume (Vt) was estimated at
the relative pressure of 0.99 (p/p0), which was the sum of Vmic and
Vmes [23]. The Raman spectra were obtained on a HORIBA LabRAM
(HR800) with HeNe laser of 532 nm. The intensity of the bands in
Raman spectra was measured using Lorentzian curve-fitting pro-
cedure. The elemental analysis (EA) was measured by PerkinElmer
2400 Series II analyzer. X-ray photoelectron spectroscopy (XPS, PHI
5000 VersaProbe II) was conducted to identify surface elemental
composition. Thermogravimetric analysis (TGA) was performed on
a STA-449-F3 analyzer under air atmosphere with heating rate of
10
C/min.
2.4. Electrochemical measurement
The EDL performance of all samples was measurement at room
temperature using a two-electrode system. The working electrodes
were prepared by mixing 80 wt % active material, 10 wt % acetylene
black, and 10 wt % polyvinylidene fluoride (PVDF), with a certain
amount of N-Methyl-2-pyrrolidone (NMP). The obtained slurry was
coated on stainless steel and dried at 80
C overnight. The coated
foils were subsequently punched into disks of 12 mm in diameter
and the mass loading of the active materials in each electrode was
about 0.8 mg 6 M KOH was used as the electrolyte. Cyclic voltam-
metry (CV) and galvanostatic charge-discharge (GCD) experiments
were conducted with a solartron electrochemical workstation.
Electrochemical impedance spectroscopy (EIS) experiments were
studied on a bio-logic VMP3 electrochemical workstation. The
specific capacitance of electrode material was calculated according
to equation (1):
2I Dt
Cs ¼ (1)
mDV
where I is the response current (A), DV is the voltage change
excluding the voltage drop during the discharge process (V), Dt is
the discharge time (s), and m is the weight of the active material in
each electrode. To evaluate electrical conductivity, the sample
powders mixed well with 10 wt % PVDF binder and moderate NMP
were pressed into a PET (Polyethylene terephthalate) thin film,
26 P. Liu et al. / Carbon 152 (2019) 24e32
dried at 80
C overnight. The coated films were subsequently
punched into disks of 12 mm in diameter and the samples were of
10e20 mm in thickness. Then the film resistances were measured
using a four-point electrical probe (Pro4 from Lucas Laboratories).
3. Results and discussion
Amorphous carbon is a disordered aggregate of micro-graphene
domains, which correlate each other via sp3 carbons or oxygenates.
According to the hierarchical domain structural model, a graphi-
tizable amorphous carbon is consisting of micro-domains partially
merged to each other, while a non-graphitizable is a carbon ma-
terial of graphene domains free from each other [24]. In this work,
ammonia can reduce part of oxygenates and correlate micro-
graphene domains in the same plane by generating polypeptide
species and thereby facilitate the graphitization process and the
mechanism is shown in Fig. 1.
Fig. 2 shows the HRTEM images of AC, non-NH3 hydrothermal
and NH3-hydrothermal samples. As shown in Fig. 2 (a), the pristine
AC is amorphous agglomerate. From Fig. 2 (bec), non-NH3 hydro-
thermal treatment at 200
C led to the formation amorphous
lamellar species. However, Fig. 2 (d)-(f) indicate that the NH3-
assisted hydrothermal treatment resulted in the formation multi-
layer graphene of 1e5 nm in thickness, which was also consoli-
dated by the AFM results in SI file (Fig. S1). The corresponding FFT
pattern of crystallite in Fig. 2 (e) clearly verifies the crystalline of
few layer graphene. These results all suggested that hydrothermal
process could induce the re-distribution of the basic unit of
amorphous AC to form lamellar graphene. As shown in Fig. 2 (f), the
morphology of large piece graphene (two layers) synthesized by
NH3-hydrothermal method is obvious, indicating a successful
transformation from amorphous carbon to multilayer graphene.
N2 sorption isotherms and pore size distribution (PSD) curves of
AC, NG and HTAC samples are shown in Fig. 3. The specific surface
area (SSA), pore volume, and pore size distribution of the samples
Fig. 1. Graphitization mechanism of AC to NG. (A colour version of this figure can be viewed online.)
Fig. 2. HRTEM images of AC (a); non-NH3 hydrothermal (bec) and NH3-hydrothermal (def) samples.
were calculated, and the results are shown in Table 1. As illustrated
in Fig. 3 (a), all nitrogen adsorption isotherms could be considered
as a combination of type I and IV, which is evidenced by consid-
erable porosity and high surface area [25,26]. From Fig. 3 (a), the
major uptake of nitrogen absorption occurred at a relative pressure
below 0.2 and the curve at high pressure was horizontal, implying a
micropore-predominant structure of AC and NG. The hysteresis
loops indicated the existence of some mesopores in the samples
[27], which were also consolidated by the multi-peaks in PSD
curves in Fig. 3 (b). NG showed a sharply decrease in SSA and total
volume compared with AC which was associated with the rear-
rangement of carbon atoms to more regular lamellae multi-layer
graphene species during the ammonia hydrothermal process.
Moreover, the SSA and pore volume of NG were 1424 m2 g1 and
0.56 cm3 g1 which were significantly higher than those of gra-
phene prepared by Hummers' method [28] and Hofmann method
[29].
Raman spectroscopy can be efficiently used to monitor the
number of layers, quality of layers, doping level and confinement in
graphene nanostructures. The Raman spectra of samples are shown
in Fig. 4 (a). All samples presented both the D band and G band. The
D band is associated with disordered samples or graphene edges,
while the G band is the result of the first-order scattering of the E2g
mode of sp2 carbon domains [30,31]. As shown in Fig. 4 (a), the
characteristic D and G bands of NG are at 1348 and 1580 cm1. The
ratio of D-band (ID) to G-band (IG) (ID/IG) of pristine AC is 1.82,
evidencing there were many defects in amorphous AC [32]. Water
treatment could eliminate some defects in the AC as indicated by
the lowered ID/IG (1.25) arising from the reactions between H2O and
active carbon sites. There is a non-negligible 2D peak on the Raman
spectrum of the water treated sample, which also verifies that
hydrothermal treatment can remove part of active sp3 carbon.
Therefore, non-ammonia hydrothermal treatment also may lead to
the lamellar carbon of sp2 domain aggregates although the carbon
is amorphous. After NH3-assisted hydrothermal treatment, the ID/IG
 P. Liu et al. / Carbon 152 (2019) 24e32 27

Fig. 3. Nitrogen sorption isotherms (a) and pore size distributions (b) of the AC (black), NG (red) and HTAC (blue) samples. (A colour version of this figure can be viewed online.)

Table 1
Textural properties of the AC and its derived NG and HTAC samples.

Sample SSAa (m2 g1) Vbtot (cm3 g1) Vbmic (cm3 g1) Vbmes (cm3 g1) ID/IG Dd (nm)

AC 2407 1.57 0.55 1.02 1.82 1.22

NG 1424 0.86 0.36 0.50 0.84 1.21
HTAC 2000 1.24 0.49 0.75 1.25 1.22
a
SSA calculated by the BET method.
b
Total, micro- and meso-pore volume from N2 sorption test.
c
Intensity ratio of the G band and D band in Raman spectra.
d
Pore widths at the main maxima of PSD.

value of the NG sample was dramatically decreased to 0.84 due to
the crystalline of the lamellae species. The broad 2D peak at
2673 cm1 also verified the formation of few-layered graphene
rather than single-layer graphene in NG [33].
The FTIR spectra of AC and NG are shown in Fig. 4 (b). The peaks
of the oxygenate groups on NG such as carboxyl (1100-1200 cm1)
and C¼O (1450 cm1) decreased remarkably compared those on
pristine AC, suggesting the deoxygenation of AC by ammonia dur-
ing hydrothermal process. However, the phenol groups (1024-
1033 cm1) were only slightly changed. Moreover, new peaks
ascribed to peptide (1642 cm1) [34] appeared on NG, which could
be ascribed to the reaction between amine groups and carboxyl
groups. In addition, a peak corresponding to NeH (1458 cm1) is
found in NG.
XPS was used to determine the nature of the carbon bonds
presented on the surface of AC, NG and HTAC samples. In addition
to the carbon and oxygen peaks, a nitrogen peak clearly existed in
the XPS survey scan spectrum of NG (Fig. 5 (a)). As shown in Fig. 5
(b), the C 1s spectrum of AC presents a sharp peak at 284.8 eV
corresponding to the CeC bonds. AC was obtained from highly ar-
omatic precursor, and an unobvious peak at 284.2 eV related to the
C¼C bonds is found. Other peaks correspond to various CeO
bonding configurations could also be found, including the CeO
bonds, carbonyls (C¼O), and carboxylates (O¼CeO) at about
286.5, 289.1 and 291.2 eV, respectively. When nitrogen atoms were
doped into graphene, peaks at the C 1s spectrum would change
accordingly [35,36]. After hydrothermal treatment in ammonia, NG
(Fig. 5 (c)) shows new peaks in the C 1s spectrum at 284.2 eV and
286.2 eV correspond to the sp2 carbon of C¼C bonds and the carbon
of CeN. And the intensity of the peak ascribed to the CeO bonding

Fig. 4. Raman spectra (a) and FT-IR spectra (b) of AC (black), NG (red) and HTAC (blue). (A colour version of this figure can be viewed online.)
28
configuration shifted to a much lower value (Table 2). The carbon
related bonds on the NG sample consisted of a smaller amount
(15.3 %) of carbonyl groups (C¼O) and carboxylic groups (HOeC¼O)
compared with that of AC (27.5 %), proving that part of the
oxygenate groups in AC were removed by ammonia. The N 1s
spectrum is usually used to determine the nitrogen configurations.
From Fig. 5 (d), the peaks at 399.0 eV and 402.2 eV are assigned to
pyridinic N (N1) and quaternary N (N2) [37]. No other nitrogen
related bonds could be found. It is found that NG contains sp2- (49.6
%) and sp3- (27.3 %) hybridized carbon atoms as well as pyridinic N
(0.7 %) and quaternary N (1.3 %) (Table 2), showing a sp3/sp2 ration
of 0.55, consisting with the Raman ID/IG value. Elemental compo-
sitions from EA data for the samples are listed in Table 3. The ox-
ygen content of NG sample decreased from 20.61 % of AC to 13.06 %,
because that part of the oxygenate groups in AC was removed by
ammonia.
The mechanism of phase transition of amorphous carbon to
multilayer graphene was further discussed. GC is usually composed
of planar shaped poly-condensed aromatic compounds containing
many oxygenate groups. These basic units stack in a parallel and
regular pattern of two dimensions [38]. The oxygenate groups and
sp3 carbon atoms in AC correlate with each other to form 3D
framework. Hydrothermal treatment can remove part of active sp3
carbons via the reaction in equation (2):
C þ H2 O /CO þ H2
Therefore, non-ammonia hydrothermal treatment may also lead
to the lamellar carbon although the carbon is amorphous. However,
Fig. 5. XPS spectra of AC, NG and HTAC (a); high resolution C 1s XPS spectra of AC (b), NG (c); high resolution N 1s XPS spectrum of NG (d). (A colour version of this figure can be
viewed online.)
P. Liu et al. / Carbon 152 (2019) 24e32
non-ammonia hydrothermal treatment cannot remove the
oxygenate groups to a satisfied level because that the oxidation of
molecules would result in the incomplete sintered connection of
closely packed micro-domains, leading to the strongly wrinkled
structure of HTAC [39]. Yoon et al. reported a hierarchical domain
structural model describes a sequential development from carbon-
containing molecules to bulk graphite material [38,39]. GC is a
carbon material of domains consisting of micro-domains partially
merged to each other. The connection between micro-domains
after heat treatment (2800
C) resulted in domain size larger than
20 nm [24,39]. However, the temperatures for deoxygenation var-
ied in case of oxygenate groups. Temperatures higher than 700
C
were needed for the removal of ether, quinone, carbonyl and
phenol groups, which could also be consolidated by TGA results
from Fig. S2.
Here, we can consider the basic unit of amorphous carbon was
disorderly stacking of nano-graphene oxide (GO) (or graphite
nanocrystallite). GO was considered as a large, functionalized
graphene-like sheet physically adsorbed with lots of small, highly
oxidized debris (OD) that could be washed away under alkaline
conditions [40]. Lu and He recently reported the extraction of
oxidized debris in graphene in the presence of ammonia [41]. They
suggested that the reduction of GO probably originated from the
nucleophilic attack of NH3 or OH. Hu et al. [42] synthesized gra-
phene quantum dots from oxidized debris by hydrothermal treat-
(2) ment of graphene oxide at 180
C in the presence of ammonia. Yang
et al. [43] reported a NH3-assisted semi-carbonization of carbon
aerogel. They found that nitrogen functional groups with high
 P. Liu et al. / Carbon 152 (2019) 24e32
Table 2
The contents of chemical bonds in AC and NG derived from XPS data.a
Sample AC
C¼C (%) 3.2
CeC (%) 50.3
CeN (%) e 8.8
CeO (%) 17.2
C¼O (%) 6.8
OeC¼O (%) 3.5
sp2 (%) 3.2
sp3 (%) 67.5
sp3/sp2 ration 21.0
pyridinic N (%) e 0.7
quaternary N (%) e 1.3
a
The sp2-hybridized carbon was calculated according to the quantity of C¼C in
the XPS and the sp3-hybridized carbon was calculated by the total single bonds with
C including CeC, CeO and CeN. All data are normalized to carbon content.
thermo-decomposable ability like pyrrolic/pyridine can be intro-
duced into the semi-carbonized aerogel framework by substituting
oxygen functional groups with low thermo-decomposable ability
like C¼O quinone-type groups. Their results gave us indications of
how to lower down the temperature for the removal of oxygenate
groups on AC. Feng et al. [44] prepared reduced graphene oxide by
using NaeNH3 treatment with active solvated electrons as the
highly reductive agent because metallic sodium can be dissolved in
liquid ammonia to create a blue solution with strong reducibility
due to the generation of ‘solvated electron e[NH3]n’. The solvated
electrons in sodium-ammonia solution can effectively remove the
oxygen from graphene oxide to produce reduced graphene oxide
samples with an oxygen content of 5.6 wt % [44]. However, their
productions also had very weak 2D Raman peaks. From these two
reports, there was strong indication that ammonia could replace
the oxygen groups in the graphene oxide (or graphite) and pro-
vided solvated electrons to reduced graphene oxide. However, the
transition of amorphous carbon to graphene in the presence of
ammonia was still unclear.
In our work, we also did the similar hydrothermal experiments
by totally or partly replacing ammonia by NaOH while maintain the
same pH value of solution, or lower down the ammonia concen-
tration in the solution. And the XRD profiles and Raman spectra of
samples are shown in Fig. 6 and Fig. S3. From Fig. 6, the X-ray
diffraction pattern of AC is a composite of a broad profile at
2q ¼ 15e30
assigned to amorphous carbon and a sharp profile
from the nano-graphite basic unites (2q ¼ 26.5
), indicating that
the AC sample was the 3D framework of oxygenate groups on edge
of nano-graphite and sp3 carbons correlating each other. NaOH-
assisted hydrothermal treatment of AC cannot obtain the graphi-
tization of amorphous carbon as indicated by the broad peak at
2q ¼ 15e30
. Interestingly, hydrothermal treatment of AC by solely
water (HTAC) led to the disappearance of amorphous carbon
leaving only nano-graphite via reaction (2) as indicated by the
horizontal background and weak diffraction peak at 2q ¼ 26.5
. The
peak at 2q ¼ 26.5
over NG is the sharpest one of all samples,
suggesting the crystal growth in size of multi-layer graphene units.
From Fig. S3, the Raman spectra could give us the same information
Table 3
Elemental compositions (wt %) of AC, NG and HTAC from EA data.
Samples Elements (wt %)
C O N H
AC 66.67 20.61 0.29
NG 68.26 13.06 1.50
HTAC 70.93 18.95 0.31
29
that the essential condition in graphitization of AC to multilayer
graphene via ammonia-assisted hydrothermal method was the
NG high concentration of ammonia in solution.
49.6 Combining the results from XRD, FTIR, Raman and XPS, we as-
13.9 sume the graphitization mechanism of AC to NG, which is shown in
4.6
Fig. 1: 1) in the framework of AC, there were plenty of oxygenate
8.1 groups on edge of nano-graphite basic units correlating with sp3
2.6 carbon. The sp3 carbons could be erased by reaction (2) during the
49.6 hydrothermal process to generate nano-graphite basic units with
27.3
plenty of oxygenate groups; 2) Part of oxygenates were replaced by
0.55
NH3 to form amine groups on the unites; 3) the amine groups
reacted with carboxyl groups to form polypeptide species during
ammonia-assisted hydrothermal process, which was the key step in
graphitization; 4) the decomposition of polypeptide species trig-
gering the crystal growth of nano-graphite unites. However, the
terminal phenol groups cannot be replaced by NH3. They could only
form ether groups as the defects in multilayer graphene. Therefore,
reducing the phenol groups on amorphous carbon would help to
reduce the defects in final products. Furthermore, the phenol
groups could react with NaOH to form PhONa species which could
inhibite the formation of strong bonds between isolated nano-
graphite crystalline unites. That was why replacing ammonia by
NaOH cannot achieve the same results. On the other hand, peptides
bonds could lead to contiguous nano-graphite unites in same plane
and easily decompose at high temperature to generate fresh in-
terfaces triggering the crystal growth of nano-graphite unites. High
concentration of ammonia in solution would provide electron-rich
condition to accelerate crystal growth rate of nano-graphite unites.
Therefore, lower down the concentration of ammonia in solution
would remarkably reduce the graphitization effect of ammonia due
to the fast hydrolysis of peptides bonds. Amorphous carbon is a
disordered aggregate of micro-graphene domains, which correlate
each other via sp3 carbons or oxygenates while the obtained multi-
layer graphene is the multilayer-stacking of larger graphene sheets
via p-p electron interaction.
Finally, EDL performance was tested. Well crystalline graphene
had higher electrical conductivities and mechanical properties than
AC due to stacking regularity of the hexagonal carbon layers,
leading to a fast electron transfer and reduced number of defects
[45]. EDL performance of the resultant carbon materials was
1.08
0.89
Fig. 6. XRD patterns of AC and other different samples treated with ammonia, NaOH
1.11
and water, respectively. (A colour version of this figure can be viewed online.)
30
Fig. 7. CV curves at a scanning rate of 2 mV s1 (a); GCD curves at current density of 1 A g1 (b); Specific capacitances as a function at various current density ranging from 0.5 to
20 A g1 (c) and Nyquist plots (d) of the AC and its derived NG and HTAC. (A colour version of this figure can be viewed online.)
evaluated with two-electrode system using 6 M KOH as electrolyte.
Fig. 7 (a) shows the CV performance of all samples at the scanning
rate of 2 mV s1. For an ideal symmetric supercapacitor, the trans-
port of ions is not limited. The curve of current versus voltage will
be rectangular-shaped when CV testing is measured at a certain
scanning rate [46]. It is obvious to see that the AC and its derived NG
and HTAC electrode materials exhibited quasi-rectangular shape for
CV curves, indicating the typical double layer capacitance. Fig. 7 (b)
shows the GCD curves at a current density of 1 A g1, which all
exhibit nearly symmetric triangular shape with an insignificant
voltage drop during discharge time, indicating a good conductivity.
The symmetrical charging and discharging curves without obvious
pseudo-capacitance behavior are the typical characteristics of ideal
double layer capacitors, which implied the good reversibility in
adsorption and desorption of the electrodes. And the voltage drops
of all curves indicate that all electrodes have a small internal
resistance. This could be attributed to the ions transport process at
a high voltage. Specifically, as shown in Fig. 7 (c), we noted that at
low electric current densities (e.g.0.5 A g1), specific capacitance, a
quantitative characteristic of the ability of charge accumulation,
depended primarily on the SSA and varied in the order
AC > HTAC > NG. However, as the current density increased, the
specific capacitance of AC decreased very rapidly. In contrast, the
graphene NG sample showed a moderate decrease rate in capaci-
tance. The NG sample could have a specific capacitance of 138 F g1
at current density up to 10 A g1, which is much larger than the AC
sample. These could be due to the hydrophilicity of carbon mate-
rials by doping N element, providing more active sites for electro-
lyte ions. Therefore, the N-modification can enhance the ion
adsorption capacity of multilayer graphene electrodes. At low
P. Liu et al. / Carbon 152 (2019) 24e32
current density, the electrolyte ions had sufficient time to infiltrate
into the interior of the electrode materials, and the effective
adsorption SSA is essential. At high current density, the ion infil-
tration time was short. N-doped multilayer graphene provided ion
channels for the ions adsorption and migration due to the removal
of part of sp3 carbon and oxygenates by ammonia treatment. And
the cycle stability performance at 1 A g1 after 10000 cycles is
shown in SI file (Fig. S4). This superior rate performance should be
attributed to the good conductivity of ultrathin graphitic nano-
structures. NG displayed the best conductivity (75 S m1), which
was significantly higher than the conductivity of the AC (42 S m1).
This enhancement could be attributed to the graphitization of AC
and the doping effect of electron-rich N in a graphitic layer. The
conductivity of HTAC (39 S m1) was similar to AC which may due
to amorphous character of HTAC [47]. This could also be proved by
EIS Nyquist plots, shown in Fig. 7 (d). All electrodes show apparent
semicircles in the high frequency region. It is obvious to see that NG
sample has the lowest resistance of 3.2 Ohm, indicating best con-
ductivity. Moreover, owning to its ultrathin conductive network
and large SSA, the NG sample had much larger specific capacitance
than the other reported NGs prepared by catalytic graphitization
(usually less than 100 F g1 at 10 A g1) [48e50].
To verify the universality of the method, we also treated the
commercial graphene nanosheet (GS) by the same method. Inter-
estingly, the defect intensity of GS was remarkably reduced, and N-
doping to the frame of GS was found. However, the exfoliating ef-
fect on graphene nanosheet in Ref. [51] was not obvious. The
characterizations of NGS sample are shown in SI file (Fig. S5 and
Table S1).
As shown in Fig. 8, the GCD curves show little internal resistance
 P. Liu et al. / Carbon 152 (2019) 24e32
Fig. 8. The EDL characterizations of the NH3-assited hydrothermal graphene nanosheet (NGS) sample. (A colour version of this figure can be viewed online.)
(IR) drop, demonstrating the good electronic conducting proper-
ties. NGS displayed a conductivity of 1150 S m1, about 1.5 times
higher than the conductivity of the reference GS (802 S m1) which
was also consistent with the EIS test results (Fig. 8 (d)).
However, only small specific capacitance of 22 F g1 at 0.1 A g1
could be obtained using NGS due to the low surface area and small
pore volume. This result verifies the advantage of our method in
obtaining nitrogen-doped graphene with high surface area and
large pore volume from activated carbon for high performance
supercapacitors.
4. Conclusions
Multilayer graphene had been prepared via ammonia-assisted
hydrothermal method using amorphous AC as raw material at a
low temperature without any metal catalyst. The obtained ultrathin
graphite nanostructure was composed of 2e10 layers, forming a
good conductive network on the carbon framework, which could
be used as promising electrodes. We reveled the mechanism of the
phase transition of amorphous carbon to multi-layer graphene that
ammonia can replace part of oxygenate species and react with
carboxyl groups to generate peptide bonds which can lead to
contiguous nano-graphite unites in same plane and easily decom-
position at high temperature to trigger the crystal growth of nano-
graphite unites. The results in this work provide a new concept to
synthesize mass graphene in relative mild conditions.
31
Acknowledgement
The authors would like to acknowledge the National Key
Research and Development Program of China for financial support
of JCYJ20170817161720484.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2019.05.082.
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