international journal of hydrogen energy xxx (xxxx) xxx

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Sulfur encapsulated in nitrogen-doped graphene

aerogel as a cathode material for high performance
lithium-sulfur batteries

Yan Jia, Yi-Song Zhao, Xiao-Xiao Yang, Meng-Xin Ren, Yu-Qian Wang,
Bu-Yue Lei, Dong-Lin Zhao*
State Key Laboratory of Chemical Resource Engineering, Key Laboratory of Carbon Fiber and Functional Polymers
(Beijing University of Chemical Technology), Ministry of Education, Beijing Engineering Research Center of
Environmental Material for Water Purification, Beijing University of Chemical Technology, Beijing, 100029, China

highlights graphical abstract

N-GA/S composites were synthe-

sized by a facile method.

The pyridinic-N can reduce loss of
active substances and inhibit
shuttle effect.

Nitrogen-doped graphene aerogel
can reduce the volume effect.

article info abstract

Article history: Lithium-sulfur batteries are considered to be an ideal high-performance rechargeable

Received 9 June 2020 lithium battery. However, some problems have seriously hindered the practical application
Received in revised form of lithium-sulfur batteries. A simple one-step hydrothermal method has been applied to
20 November 2020 design nitrogen-doped graphene aerogel (N-GA) with three different nitrogen sources.
Accepted 22 November 2020 Subsequently, sulfur was encapsulated in N-GA by chemical deposition method to syn-
Available online xxx thesize sulfur encapsulated in N-GA (N-GA/S) composites. Among them, the N-GA1/S
composite with sulfur content reaching 75.5 wt% has a discharge specific capacity of
Keywords: 723.9 mAh g1 after 100 cycles at 0.7 C, and the capacity retention rate is up to 87.4% while
Nitrogen-doped graphene the coulombic efficiency still remains 98%. The outstanding electrochemical performance
Sulfur cathode is owing to the good coating of sulfur by nitrogen-doped graphene aerogel, the improve-
Aerogel ment of the conductivity of the graphene skeleton by nitrogen doping, and the strong
Cycling stability adsorption capacity of the doped nitrogen atom to lithium polysulfide. The graphene
Lithium-sulfur batteries skeleton also helps to reduce the volume effect while charging and discharging. Further-
more, the proportion of pyridinic-N in N-GA1/S composites is higher than that in the two
other composites, and it has a better adsorption capacity for lithium polysulfide.

* Corresponding author.
E-mail address: dlzhao@mail.buct.edu.cn (D.-L. Zhao).
https://doi.org/10.1016/j.ijhydene.2020.11.199
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Jia Y et al., Sulfur encapsulated in nitrogen-doped graphene aerogel as a cathode material for high perfor-
mance lithium-sulfur batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.11.199
2 international journal of hydrogen energy xxx (xxxx) xxx
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
With the rapid growth of the population, the triumph of the
economy, and the improvement of people’s living standards,
human demand for energy is increasing. Along with the dra-
matic increase in fossil energy consumption, the resulting
environmental problems are even more worrying. In order to
reduce these environmental problems and decrease the heavy
dependence on fossil energy, developing energy sources that
use green energy is extremely urgent. Therefore, the
economical and efficient storage of electrical energy is
essential for the further promotion of renewable energy. A
rechargeable battery is a suitable choice for storing electrical
energy. As an “over lithium-ion” battery system, lithium-
sulfur batteries have a theoretical specific capacity of
1675 mAh g1, which is one order of magnitude higher than
that of transition metal oxide cathode materials, and sulfur is
one of the most plentiful elements in the earth’s crust [1e3].
Researchers have been studying lithium-sulfur batteries
for decades. Although researchers have devoted a lot of effort
to make significant progress in this area, they are still unable
to commercialize them like lithium-ion batteries. Poor cyclic
performance is a major obstacle to its application. The reason
is the non-conductivity of sulfur, the solubility of polysulfides
and the resulting shuttle effect and the remodeling and
destruction of material structure [4e6]. In the past few years,
the types of sulfur cathode materials have become diversified
through microstructure design and application of different
materials, such as metal oxide/sulfur composite cathode
materials [7e9], polymer/sulfur composite cathode materials
[10e12], and carbon/sulfur composites [13e16]. These changes
have made the sulfur cathode material a promising achieve-
ment in terms of enhancing cycle stability and increasing
capacity. The study on cathode materials of lithium-sulfur
batteries focuses on carbon/sulfur composite materials.
Carbon-based materials have a wide variety of structures,
including nanoporous carbon [17e19], carbon nanotubes
[20e22], graphene [23e26], and many other forms of carbon.
These carbon materials have excellent electrical conductivity,
good chemical and physical stability. The conductivity of the
sulfur cathode is obviously improved through the combina-
tion of sulfur and carbon materials. Due to the adsorption
capacity of the carbon material, the polysulfide dissolution
into electrolyte can be restrained to a certain extent, and the
electrochemical performance of the sulfur cathode material is
greatly improved [27,28].
Graphene is widely recognized for its large surface area,
leading electrical conductivity, high strength, and good flexi-
bility. When combined with sulfur, it can improve the per-
formance of lithium-sulfur batteries. Researchers have
illustrated that aqueous dispersions of graphene oxide can
form a three-dimensional columnar hydrogel by self-
Please cite this article as: Jia Y et al., Sulfur encapsulated in nitrogen-doped graphene aerogel as a cathode material for high perfor-
mance lithium-sulfur batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.11.199
assembly under hydrothermal conditions [29]. Recent
studies have found that graphene doped with heteroatoms
can be more effective in improving the performance of sulfur
cathodes when combined with sulfur [30]. Among various
doping elements (nitrogen, boron, phosphorus, and sulfur),
nitrogen doping has become the most interesting doping
element because it can greatly improve the surface polarity,
wettability and electrical conductivity of carbon materials
[31,32]. Song et al. added cyanamide to an aqueous dispersion
of graphene oxide, uniformly mixed at 80  C, and evaporated
to dryness to a powder. The powder was heated to 900  C in a
mixed gas of hydrogen and argon, and held for 2 h to wait for
highly pleated nitrogen-doped graphene. The composite ma-
terial obtained by compounding with sulfur was excellent in
cycle performance [33]. The conductivity of graphene can be
improved by nitrogen doping. And the doped nitrogen atom
has good adsorption capacity for polysulfide, which restrains
the shuttle effect and improves the cycle stability of sulfur
cathode material to a great extent [34].
In this work, we prepared three kinds of sulfur encapsu-
lated in nitrogen-doped graphene aerogel (N-GA/S) composite
cathode materials using ethylenediamine, urea and ammonia
as nitrogen sources. The preparation scheme is shown in
Fig. 1. Nitrogen-doped graphene aerogel was prepared by the
hydrothermal method and then combined with sulfur to
obtain the N-GA/S composites. The excellent electrochemical
performance of the composite material is due to the following
reasons. Firstly, the micro-nanocrystallization of sulfur par-
ticles can increase the contact area of elemental sulfur with
the carrier material and the electrolyte, which is beneficial to
charge transport and the diffusion of lithium-ion, increase the
utilization rate of the active substances, and enhance rate
performance. Secondly, the coating of sulfur particles by
graphene aerogel can restrain the shuttle effect and enhance
the cycle stability. Graphene has excellent electrical conduc-
tivity, and the combination with sulfur can increase the
electrical conductivity of the composite positive electrode
material. The large specific surface area of graphene is
conducive to the loading of sulfur particles on graphene,
forming a good composite and effectively limiting the disso-
lution and diffusion of polysulfides. Graphene has excellent
flexibility and rich pleats, which is beneficial to alleviate the
effects of volumetric effects. The third is that due to the
support of a three-dimensional structure, graphene is not
easy to agglomerate, and the three-dimensional network
cladding structure is also beneficial to limit the shuttle effect.
Finally, nitrogen doping can improve the conductivity of gra-
phene, and has good adsorption capacity for polysulfides,
which can effectively improve the cycle performance of
composite cathode materials.
 international journal of hydrogen energy xxx (xxxx) xxx
Fig. 1 e Schematic illustration of the synthetic route for N-GA/S.
Experimental
Synthesis of GO
We prepared graphene oxide (GO) using the modified Hum-
mers’ method [35]. 1 g flake graphite and 1 g NaNO3 were
mixed in 48 mL concentrated H2SO4 and continuously stirred
for 30 min under an ice bath. Successively, 6 g KMnO4 gradu-
ally added to the mixture in three portions, further stirring
continued for 90 min in an ice bath. The solution was trans-
ferred to a water bath at 35  C for 2 h, then removed from the
water bath, stirred rapidly at room temperature, and slowly
added 40 mL of deionized water. The resulting solution was
stirred in a water bath at 90  C for 20 min and then removed
from the water bath. Under stirring, deionized water (100 mL)
and hydrogen peroxide (5 mL) was added, followed by stirring
for 10 min. After centrifugation with 4 wt% dilute HCl, ob-
tained product washed by deionized water through centrifu-
gation until the pH of supernatant close to neutral. The
centrifuged product was added to 250 mL deionized water,
and after ultrasonication for 7 h, the bottom precipitate was
removed by centrifugation at 8000 r/min, and lyophilized to
obtain fluffy graphene oxide.
Synthesis of N-GA
The reduction of the graphene oxide and the nitrogen doping
can be simultaneously performed by preparing the nitrogen-
doped graphene aerogel by a facile one-step hydrothermal
method. Nitrogen-doped graphene aerogel is prepared using
ethylenediamine, urea and ammonia as nitrogen sources.
Disperse 60 mg graphene oxide in 60 mL water and sonicate
for more than 2 h to obtain a uniform aqueous dispersion of
graphene oxide. Then add 1.5 mL ethylenediamine or 12 g
urea, stir vigorously for 10 min, transfer to a 100 mL hydro-
thermal kettle, and incubate at 180  C for 12 h. Upon cooling,
the product is filtered and washed several times until the
filtrate is neutral and then freeze-dried. The nitrogen-doped
graphene aerogel having a nitrogen source of
Please cite this article as: Jia Y et al., Sulfur encapsulated in nitrogen-doped graphene aerogel as a cathode material for high perfor-
mance lithium-sulfur batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.11.199
3
ethylenediamine and urea is labeled as N-GA1 and N-GA2,
respectively. The graphene (G) was prepared in the same
manner except that no nitrogen source was added and finally
freeze-dried. There are some differences in the steps to pre-
pare the N-GA3/S composites. 40 mg graphene oxide was
added to 24 mL deionized water and sonicated for 3 h to evenly
disperse. Then add 60 mL ammonia water, stir for 30 s,
transfer to a 100 mL hydrothermal kettle, and heat at 200  C
for 12 h to obtain nitrogen-doped graphene aerogel (N-GA3)
with nitrogen source as ammonia water.
Synthesis of N-GA/S and G/S
A nitrogen-doped graphene aerogel encapsulated sulfur
composite was synthesized via chemical deposition. 4.964 g
Na2S2O3$5H2O and 0.5 g Triton X-100 were dissolved in 500 mL
deionized water, and 0.075 g N-GA1 was added and ultrason-
ically dispersed for more than 3 h. So as to deposit sulfur
particles on the surface and internal space of the nitrogen-
doped graphene, 35 mL 0.5 M concentrated hydrochloric acid
was slowly added dropwise under stirring, and the dropping
time was about 20 min. After 6 h of reaction, the product was
washed by vacuum filtration with deionized water and
ethanol, and the sample obtained after vacuum drying at 50  C
for 24 h was named N-GA1/S. The same procedure was used to
prepare N-GA2/S, except that the nitrogen-doped graphene
used was exchanged for 0.075 g N-GA2.
The N-GA3/S composite was also synthesized by chemical
deposition, but the steps were different. The mixture of 0.076 g
N-GA3 and 200 mL deionized water was ultrasonicated for
6.5 h to make the dispersion of N-GA3 in water more uniform.
Then 8.285 g Na2S2O3$5H2O was added. After stirring and
dissolving, slowly add 420 mL 0.05 M concentrated dilute hy-
drochloric acid under continuous stirring for 60 min and
continue stirring for 10 min after the addition. After standing
for 10 min, the upper layer of milky white liquid was dis-
carded, and then 400 mL of deionized water was added. After
standing for 10 min, the upper layer of milky white liquid was
discarded again, and the black precipitate at the bottom was
repeatedly vacuum filtered with deionized water to pH value
4 international journal of hydrogen energy xxx (xxxx) xxx
is neutral. The product was dried at 60  C for 12 h and obtained
the N-GA3/S sample.
The graphene/sulfur composite cathode material is pre-
pared by heating and melting method. The elemental sulfur
and graphene were weighed according to a mass ratio of 4:1,
mixed and ground for 1 h, and the sample G/S was obtained in
a nitrogen atmosphere at 155  C for 12 h.
Materials characterization
Scanning electron microscopy (SEM, Hitachi S-4700) and
transmission electron microscopy (TEM, JEOL JEM-3010) were
used to characterize the morphology and fine structure of the
material. The crystal structure of the material was charac-
terized by X-ray diffraction (XRD, Rigaku D/Max-2550). We
used X-ray photoelectron spectroscopy (XPS, Thermo Fisher
ESCALAB 250xi) to characterize the chemical environment
and elemental content of atoms in the surface layer of the
material. Thermogravimetric analysis (TGA, SDT Q600) was
carried out when the sulfur content in the composite was
measured under a nitrogen atmosphere.
Electrochemical measurements
The prepared sulfur-based positive electrode material, acety-
lene black and polyvinylidene fluoride (PVDF) were mixed and
ground in a mass ratio of 7:2:1, and then an appropriate
amount of NMP was added to obtain a uniform slurry having a
suitable viscosity. The slurry was coated on an aluminum foil
with a spatula and vacuum dried at 60  C for 24 h. The disc was
cut into 14 mm diameter discs and assembled into CR2032
button cells in an argon-filled glove box. The electrolyte sol-
vent was prepared by mixing DOL and DME in a volume ratio
of 1:1, and 1 wt% of LiNO3 was added to the electrolyte. The
lithium salt was a 1 M concentration of lithium bis(tri-
fluoromethanesulfonyl)imide (LiTFSI), and the separator used
was Celgard 2400. The assembled CR2032 button cells were
tested galvanostatic charge and discharge using a battery test
system (LAND, Wuhan) at various current densities. The test
ambient temperature is room temperature and the test
voltage range is 1.5e3 V. Cyclic voltammetry (CV) testing was
performed at a scan rate of 0.1 mV/s by an electrochemical
workstation. Electrochemical impedance spectroscopy (EIS)
was carried out by an electrochemical workstation in the
range of 0.01e100000 Hz.
Fig. 2 e a) XRD patterns of the N-GA1, N-GA2, G and GO. b) XRD patterns of the N-GA/S, G/S and S. c) TGA curves of the N-GA/
S, N-GA1, G, GO, G/S and S.
Please cite this article as: Jia Y et al., Sulfur encapsulated in nitrogen-doped graphene aerogel as a cathode material for high perfor-
mance lithium-sulfur batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.11.199
Results and discussion
The XRD patterns of N-GA1, N-GA2, G and GO are shown in
Fig. 2a. It can be seen from the figure that N-GA and G prepared
by hydrothermal method all have a broad peak near 2q ¼ 25 ,
which is a diffraction peak generated by the (002) crystal plane
of graphite. None of them showed characteristic peaks of
graphene oxide in the vicinity of 2q ¼ 11 , thus demonstrating
the effective reduction of graphene oxide and the recovery of
the graphite crystal structure. Fig. 2b shows that the com-
posite material has a very sharp sulfur diffraction peak, and
the peak position is consistent with the position of sublimed
sulfur, representing that the crystallinity of sulfur is good.
Moreover, the superposition of the diffraction peak of sulfur
and the diffraction peaks of nitrogen-doped graphene and
graphene can be clearly seen, indicating that the two are
smoothly combined.
Fig. 2c shows the TGA curves of N-GA/S, N-GA1, G, GO, G/S
and S. As can be seen from the figure, GO has a weight loss of
45.9%, which is the result of the decomposition of oxygen-
containing functional groups on graphene oxide at high
temperatures. The hydrothermally prepared N-GA1 and G
have a weight loss of 10.6% and 9.3%, respectively, which is
also the result of removal of the oxygen-containing functional
groups remaining on the surface of the graphene at high
temperatures [36]. The weight loss of N-GA1 and G is much
less than that of GO, indicating that the oxygen-containing
functional group is greatly reduced after the hydrothermal
reaction, and the product is better reduced. The weight loss of
N-GA1/S, N-GA2/S, N-GA3/S, and G/S composites at 500  C was
78.1%, 56.0%, 65.6%, and 82.1%, respectively. It can be seen
from the figure that the elemental sulfur is completely lost
weight at around 300  C, so the elemental sulfur has
completely volatilized at 500  C. At this time, the remaining of
the composite material is the graphene which loses most of
the residual oxygen-containing functional groups. Based on
the weight loss data of N-GA1 and composite materials, the
sulfur content of N-GA1/S composites was calculated to be
75.5 wt%. When the temperature is higher than 400  C, the
composite material weight loss is slow, which is attributed to
the decomposition of residual oxygen-containing functional
groups on nitrogen-doped graphene and graphene [36], so the
sulfur contents of N-GA2/S, N-GA3/S, G/S composite were
51.2 wt%, 64.5 wt%, and 79.1 wt%, respectively.
Photographs of the N-GA1/S composites are presented in
Fig. 3a and b. The N-GA1/S composite has a cylindrical
appearance with a bottom diameter of about 1.7 cm and a
 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 3 e a, b) Photographs of the N-GA1/S composites. c) SEM and d, e) TEM images of the N-GA1. f) SEM and g, h) TEM images
of the N-GA1/S. SEM images of the i) N-GA2/S, j) N-GA3/S, k) G/S composites.

mass of about 150 mg. Its density is low enough to be placed
lightly on the dandelion, and the other two samples exhibit
similar appearance and density. It can be seen from the SEM
image of N-GA1 in Fig. 3c that the N-GA1 crimp winding forms
abundant pores and wrinkles, which is beneficial to the
adhesion of sulfur particles in the pores. From the TEM image
of N-GA1 in Fig. 3d and e, it can be seen that N-GA1 is a
wrinkle-rich gauze-like structure, indicating that the prepared
N-GA1 sheet is thinner and has better quality, which is
beneficial to coating sulfur particles. From Fig. 3f, it can be
seen that the N-GA1/S composite has agglomerates formed by
N-GA1 and sulfur particles, and the sulfur particles have a
diameter of about 2 mm. The formation of the agglomerates is
due to the inclusion of sulfur particles in the pores of the N-
GA1, which is advantageous for accommodating the volume
change of the positive electrode material in the electro-
chemical reaction. It can be seen from the TEM image of N-
GA1/S in Fig. 3g and h that N-GA1 is coated with sulfur parti-
cles like a soft cloth, indicating that the two form a good
coating state. In addition, a small number of exposed sulfur
particles can be seen attached to N-GA1. Similar to the N-GA1/
S composite, the sulfur particle size is also about 2 mm which
can be seen in the SEM images of the N-GA2/S (Fig. 3i). Larger
particles formed by several small particles can be seen from
the figure, and the sulfur particles form agglomerates with the
finely divided nitrogen-doped graphene N-GA2. The N-GA2
attached to the sulfur particles did not form a relatively tight
and comprehensive coating, and still more of the surface of
the particles was not covered. Fig. 3j exhibits the SEM image of
the N-GA3/S. It is obvious that the N-GA3 is a sheet-like layer
filled with wrinkles. The size of the sulfur particles that were
not well coated was about 3 mm, and N-GA3 did not recombine
well with it. After the elemental sulfur is melted, it forms a
block with the pleated sheet-like graphene G, and a large
number of elemental sulfur agglomerates to adhere around G
(Fig. 3k). Graphene has a limited coating of sulfur.
In order to investigate the N-doping effect in graphene, XPS
measurements were performed. Fig. 4a is the survey spectra
of the N-GA1/S, N-GA1, N-GA2 and GO. It can be seen that the
N-GA1, N-GA2, and N-GA1/S have obvious N 1s peaks,

Please cite this article as: Jia Y et al., Sulfur encapsulated in nitrogen-doped graphene aerogel as a cathode material for high perfor-
mance lithium-sulfur batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.11.199
6 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 4 e a) XPS survey spectra of the N-GA1/S, N-GA1, N-GA2 and GO. The C 1s XPS spectrum of the b) GO, c) N-GA1 d) N-GA2
and e) N-GA1/S. The N 1s XPS spectrum of the f) N-GA1 g) N-GA2 and h) N-GA1/S.

indicating that nitrogen was successfully added to graphene.
The presence of the S 2p and S 2s peaks of the N-GA1/S
composite indicates that the sulfur is successfully complexed
with nitrogen-doped graphene aerogel. The intensity of the O
1s peak of the three is significantly reduced compared to GO,
and the elemental content obtained from the XPS test results
(Table 1) shows that the oxygen content of GO is 30.97 at%,
while The oxygen content of N-GA1 and NG -2 is only 8.82 at%
and 10.77 at%, respectively. The oxygen content of N-GA1 and
NG -2 is greatly reduced, indicating that both have been well
reduced in the hydrothermal process. In addition, the O/C
ratio of N-GA1 is 0.108, which is 16.9% lower than that of N-
GA2, indicating that the reduction effect of N-GA1 is better. It
may be that the nitrogen source ethylene diamine used has a
better reduction effect on graphene oxide. From the C 1s
spectra of N-GA1 and N-GA2 in Fig. 4c and d, the oxygen-

Please cite this article as: Jia Y et al., Sulfur encapsulated in nitrogen-doped graphene aerogel as a cathode material for high perfor-
mance lithium-sulfur batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.11.199
 international journal of hydrogen energy xxx (xxxx) xxx
Table 1 e Carbon, nitrogen, oxygen, sulfur content, N/C
Ratio and O/C Ratio of the GO, N-GA1, N-GA2, N-GA1/S
composites from XPS measurement.
Sample C (at%) N (at%) O (at%) S (at%) N/C Ratio O/C Ratio
GO 69.03 e 30.97 e e 0.449
N-GA1 81.95 9.23 8.82 e 0.113 0.108
N-GA2 82.60 6.63 10.77 e 0.080 0.130
N-GA1/ 79.18 7.82 8.25 4.74 0.099 0.104
S well overlapped, indicating good reversibility. After two
containing functional groups of the two are significantly less
intense than that of graphene oxide (Fig. 4b). The sp2 peak
near the 284.7 eV of carbon becomes sharp, which also in-
dicates that they have a good reduction. In addition, the peak
at 285.8 eV in the figure corresponds to the CeN bond, indi-
cating the existence of strong chemical bonding between the
nitrogen element and the carbon. From the C 1s XPS spectrum
of the NG-1W/S composite of Fig. 4e, the peak at 285.7 eV has a
contribution of CeS bond in addition to the CeN bond, indi-
cating that elemental sulfur forms a chemical bond with
nitrogen-doped graphene aerogel. Fig. 5f, g, and h displays the
N 1s XPS spectra of N-GA1, N-GA2, and N-GA1/S, respectively.
Three peaks can be separated, which are pyrrolic-N peak
(399.7e399.9 eV), pyridinic-N peak (398.5e398.7 eV) and
graphitic-N peak (401.4e1401.6 eV) [37]. The three types of
nitrogen peak positions are different by 0.1e0.2 eV, which is
due to the difference in a chemical environment.
As shown in Table 1, the nitrogen contents of N-GA1 and N-
GA2 were 9.23 at% and 6.63 at%, respectively, and the former
was 39% more than the latter. It can be seen from Table 2 that
both of them have the largest proportion of pyrrolic-N, and the
proportion of pyridinic-N of N-GA1 is 28.3%, which is about
twice that of N-GA2. The difference in nitrogen content and
nitrogen distribution may affect the electrochemical perfor-
mance of the composites. The sulfur content of the N-GA1/S
composites obtained through the XPS test is only 4.74 at%,
which is far from the sulfur content of 75.5 wt% obtained by
the TGA curve (Table 1). This is due to the coating of sulfur
particles by nitrogen-doped graphene aerogel, which results
in weak signal intensity of sulfur, and the analysis depth of
XPS is usually less than 10 nm, so the sulfur content obtained
by XPS test is very low, which also reflects the better coating
effect.
The cyclic voltammetry curves of N-GA/S composites are
exhibited in Fig. 5. It can be seen from Fig. 5a that the oxida-
tion peak of the N-GA1/S composite is around 2.4 V and the
two reduction peaks are located near 2.3 V and 2.0 V,
Fig. 5 e Cycle voltammetry profile of the N-GA/S.
Please cite this article as: Jia Y et al., Sulfur encapsulated in nitrogen-doped graphene aerogel as a cathode material for high perfor-
mance lithium-sulfur batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.11.199
7
Table 2 e N distribution of the N-GA1 and N-GA2
composites from XPS measurement.
Pyridinic-N (at%) Pyrrolic-N (at%) Graphitic-N (at%)
N-GA1 28.3 62.5 9.2
N-GA2 14.7 69.6 15.6
respectively. The CV curves of the N-GA1/S composites are
rounds of CV scanning, the position of the oxidation peak is
slightly shifted, indicating that the battery polarization be-
comes smaller and the reversibility increases. The oxidation
peak consists of two closely spaced peaks, which is the result
of a multi-step reaction of the Li2S and Li2S2 oxidation pro-
cesses. It can be seen from Fig. 5b and c that the CV curve
coincidence of the N-GA2/S and N-GA3/S composite is inferior
to that of the N-GA1/S composite, indicating that the revers-
ibility is not as good as the N-GA1/S composite. As the test
progresses, the oxidation peak shifts negatively, and the
reduction peak near 2.0 V shifts positively, and the revers-
ibility is improved. The multi-step process of polysulfide
reduction leads to a small reduction peak in the first cycle CV
curve near 1.7 V (Fig. 5c). This also reflects the greater polari-
zation at this time, and the reaction can only occur at lower
potentials.
Fig. 6a shows the 50 cycle discharge specific capacity plots
for the N-GA/S and G/S composites at 0.1 C. It is clear that N-
GA1/S composites have the best performance. The initial
discharge of N-GA1/S delivered a higher discharge capacity of
1210.7 mAh g1, and then the discharge specific capacity
decreased slowly. The discharge capacity at the 50th cycle was
876.4 mAh g1, and the capacity retention rate was 72.4%. The
cycle performance of the N-GA3/S composite was slightly
worse than that of the N-GA2/S composite. The first discharge
capacity was 1104.7 mAh g1, and the discharge capacity at
the 50th cycle was 537.9 mAh g1. The first discharge capacity
of the G/S composite without nitrogen doping was
1008.6 mAh g1, and the specific capacity decreased to
449.9 mAh g1 after 50 cycles, and the capacity retention rate
was 44.6%, showing the worst cycle performance among the
four. The reason is that nitrogen doping helps to intensify the
conductivity of graphene, and has a stronger adsorption effect
on lithium polysulfide, which can improve cycle stability.
Therefore, nitrogen-doped graphene aerogel can effectively
raise the electrochemical performance of the composites.
Moreover, it can be seen from the SEM image of G/S that
graphene and sulfur particles do not form a good coating, and
more sulfur agglomeration adheres to G, which is one of the
worst performance factors.
8 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 6 e a) Cycle performance of the N-GA/S and G/S at 0.1 C. b) Rate capability of the N-GA/S and G/S. c) Cycle stability with
corresponding coulombic efficiency and d) charge-discharge profiles of the N-GA1/S at 0.7 C.

The preparation method of N-GA1/S and N-GA2/S com-
posites is similar, but the electrochemical performance of N-
GA1/S composites is better than that of N-GA2/S composites.
The reason is that in addition to the good coating effect, the
difference in nitrogen content and nitrogen distribution in the
nitrogen-doped graphene aerogel also affects the electro-
chemical performance of the material. N-GA1 has a higher
nitrogen content and a higher proportion of pyridinic-N. The
pyridinic-N has a stronger binding force with the polysulfide,
which limits the polysulfide to the surface of nitrogen-doped
graphene. A pyridinic-N is a nitrogen atom that replaces one
carbon atom in a carbon six-membered ring at the edge or
defect of graphene, and bonds with two carbon atoms to
contribute a pair of orphan electrons, and has strong binding
force with polysulfide. The pyrrolic-N is a nitrogen atom that
replaces one carbon atom in the five-membered ring of car-
bon. It devotes two p-electrons to the p-conjugated system, so
its ability to adsorb polysulfides is weaker than that of
pyridinic-N [38]. Graphitic-N is formed by a nitrogen atom
replacing a carbon atom in the plane of graphite. Since the
electronegativity of the nitrogen atom (3.04) is larger than that
of the carbon atom (2.55), the graphitic-N is considered to be
an electron acceptor [39], and the ability to adsorb polysulfide
is the weakest among the three. It can be seen that increasing
the proportion of pyridinic-N in the composite material can
adsorb polysulfide more effectively and help to improve
electrochemical performance. This explains why N-GA1/S
performs better than N-GA2/S. The performance of N-GA3/S
composites is poor, and it has a great relationship with the
degree of the composite of sulfur particles and nitrogen-doped
graphene. As exhibited in the SEM image that the distribution
of N-GA3 is loose and does not closely bind to the sulfur
particles.
The reason why N-GA1/S composites have the best per-
formance among the four is first attributed to the fact that
nitrogen doping improves the conductivity of the composites
and facilitates the electrochemical reaction. And the combi-
nation of N-GA1 and sulfur particles is better. N-GA1 has
abundant folds and pores to make it easier to combine with
sulfur particles. As revealed in the SEM image that it covers
the sulfur particles with a diameter of about 2 mm like a soft
cloth, and has the best composite effect among the four. Good
recombination is beneficial to form a good conductive skel-
eton, reduce the volume effect caused by the change of sulfur
volume during the cycle, inhibit the diffusion of polysulfide,
and optimize the cycle stability. In addition, N-GA1 has a
higher nitrogen content, and the proportion of pyridinic-N is
also higher, and a chemical bond is also formed between
carbon and sulfur. Therefore, the N-GA1/S composite has a
good adsorption effect on polysulfides, and can effectively
clamp the shuttle effect. In summary, even though the N-GA1/
S composite has a sulfur content of up to 75.5 wt%, its cycle
performance is still the best among the four.
The comparison of the rate performances of N-GA/S is
demonstrated in Fig. 6b. It is obvious that the N-GA1/S com-
posite exhibited an excellent rate performance with discharge
capacities of 1050 mAh g1、960 mAh g1、860 mAh g1、
780 mAh g1 and 610 mAh g1 at 0.1 C、0.2C、0.5C、1C and
3 C, respectively. When the current rate returns back to 0.1 C,
the discharge capacity of about 910 mAh g1 can still be ach-
ieved, showing excellent rate performance and reversibility.
The G/S composites have the worst rate performance, and the
discharge capacities at 0.5 C, 1 C, and 3 C rates are only about
380 mAh g1, 305 mAh g1, and 205 mAh g1, respectively. The
reason why the N-GA1/S composite has excellent rate per-
formance is also attributed to the better combination of

Please cite this article as: Jia Y et al., Sulfur encapsulated in nitrogen-doped graphene aerogel as a cathode material for high perfor-
mance lithium-sulfur batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.11.199
 international journal of hydrogen energy xxx (xxxx) xxx 9

As for the further improvement of the cycle performance of

N-GA1/S composites, it can be considered to optimize the
preparation process to make the composite effect of nitrogen-
doped graphene and sulfur particles better. It is also
conceivable to adjust the process for preparing nitrogen-
doped graphene so that the nitrogen content and the pro-
portion of pyridinic-N are both high. In addition, it is also
possible to improve the electrolyte, for example, adding an
additive or the like. Lithium-sulfur batteries involve positive
electrodes, negative electrodes, separators, electrolytes, etc. If
comprehensive measures are taken, the cycle stability, rate
performance, and safety of lithium-sulfur batteries can be
more effectively improved.
Fig. 7 displays electrochemical impedance spectra of N-
GA1/S, N-GA2/S, and G/S composites. As can be seen from the
Fig. 7 e EIS spectra of the N-GA1/S, N-GA2/S and G/S. figure, the impedance spectrum is mainly composed of a
straight line at a low-frequency band and a semicircle at a
high-frequency band. The line at the low-frequency band
represents the Warburg impedance (W), and the semicircle at
Table 3 e Value of component parameters of equivalent
circuit of EIS. the high-frequency band stands for the charge transfer
impedance (Rct) and the capacitance (Cd) [40]. The intercept of
N-GA1/S N-GA2/S G/S
the semicircle in the high-frequency region and the Z0 axis is
Re(U) 4.443 5.126 2.901 the contact resistance (Re) of the battery, including the elec-
Rct(U) 22.45 28.27 69.50
trolyte and the electrode material impedance. From the fitting
results Table 3, the Rct of N-GA1/S, N-GA2/S, and G/S com-
posites are 22.45 U, 28.27 U, and 69.50 U, respectively, and the
graphene and sulfur particles, and nitrogen doping improves
Re of the three is not much different. It shows that N-GA1/S
the conductivity of the composites. This further increases the
has the lowest charge transfer impedance among the three,
active site of the electrochemical reaction and can mobilize
which is most beneficial to the electrochemical reaction. The
more active substances to participate in the reaction at a large
EIS test results confirm the conclusion that the electro-
rate. In addition, the nitrogen element incorporated in N-GA1
chemical performances of N-GA1/S, N-GA2/S and G/S are
can adsorb polysulfide well, suppress the shuttle effect, lessen
successively reduced.
the loss of active substances, and stabilize the performance.
In order to test the long cycle performance of the N-GA1/S
composite at a higher current density, 100 cycles were per-
Conclusions
formed at 0.7 C (Fig. 6c). The first discharge capacity was
779.6 mAh g1, and the discharge capacity reached a peak of
In summary, we prepared N-GA through an easy one-step
828.5 mAh g1 at the 6th cycle. After that, the capacity was
hydrothermal method, and then chemically deposited it
slowly attenuated, and the discharge capacity of the 50th
with sulfur to form N-GA/S. The N-GA1/S composite exhibits
cycle was 782.0 mAh g1. The capacity retention rate was
good cycle stability. Its initial discharge specific capacity was
94.4%. By the 100th cycle, the discharge capacity was still
1210.7 mAh g1 and the capacity retention rate was 72.4% after
723.9 mAh g1, with the capacity retention rate was 87.4%. In
50 cycles at 0.1 C. The stability is better at a higher current
the whole process, except for the fluctuation of the Coulomb
density of 0.7 C, and the specific capacity of the cycle is still
efficiency of the first few cycles, it can basically maintain 98%
maintained at 723.9 mAh g1 while the capacity retention rate
or more, showing excellent cycle stability. Similarly, excellent
is 87.4%. Moreover, the N-GA1/S composite has excellent rate
long-cycle performance at higher rates is associated with
performance and good reversibility. All of this due to the good
better composite effects and good polysulfide adsorption.
combination of three-dimensional porous graphene aerogel
Fig. 6d presents the charge and discharge curves at 0.7 C. Due
and nano-sulfur particles, which effectively increases the
to the way of statistical data, the first discharge is counted as a
electron and ion migration rate, suppresses the shuttle effect,
single cycle. It can be seen from the figure that the discharge
and alleviates the volume effect. In addition, nitrogen doping
platform is located near 2.3 V and 2.0 V, respectively, corre-
can improve the conductivity of graphene. The doped nitro-
sponding to the conversion process of elemental sulfur to
gen atoms, especially the pyridinic-N, have a good adsorption
highly polysulfide (Li2Sx, 4  x  8), and further reduction to
effect on polysulfides, which can reduce the loss of active
oligomeric polysulfide (Li2Sx, 2  x < 4) and Li2S. The charging
substances and inhibit the shuttle effect, and help to enhance
platform is located between 2.25 and 2.45 V, which corre-
the stability performance.
sponds to the oxidation of Li2S2 and Li2S into elemental sulfur.
The initial discharge platform is lower, which is due to the
activation process leading to greater polarization, and then
the coincidence of the charge and discharge platform is better,
indicating excellent reversibility.

Please cite this article as: Jia Y et al., Sulfur encapsulated in nitrogen-doped graphene aerogel as a cathode material for high perfor-
mance lithium-sulfur batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.11.199
10 international journal of hydrogen energy xxx (xxxx) xxx
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgment
This work was supported by the National Natural Science
Foundation of China (Grant No. 51572012).
references
[1] Choi S, Seo DH, Mohammad RK, Zhang C, Timothy V, Han ZJ,
Bendavid A, Guo X, Yick S, Murdock AT, Su D, Lee BR, Du A,
Dou SX, Wang G. WO3 nanolayer coated 3D-graphene/sulfur
composites for high performance lithium/sulfur batteries. J
Mater Chem 2019;7:4596e603.
[2] Yao X, Huang N, Han F, Zhang Q, Wan H, Mwizerwa JP,
Wang C, Xu X. High-performance all-solid-state lithium-
sulfur batteries enabled by amorphous sulfur-coated
reduced graphene oxide cathodes. Adv Energy Mater
2017;7:1602923.
[3] Seh ZW, Sun Y, Zhang Q, Cui Y. Designing high-energy
lithium-sulfur batteries. Chem Soc Rev 2016;45:5605e34.
[4] Zhang L, Ji L, Glans P-A, Zhang Y, Zhu J, Guo J. Electronic
structure and chemical bonding of a graphene oxide-sulfur
nanocomposite for use in superior performance lithium-
sulfur cells. Phys Chem Chem Phys 2012;14:13670e5.
[5] Jayaprakash N, Shen J, Moganty SS, Corona A, Archer LA.
Porous hollow carbon@sulfur composites for high-power
lithium-sulfur batteries. Angew Chem Int Ed 2011;50:5904e8.
[6] Fang X, Peng H. A revolution in electrodes: recent progress in
rechargeable lithium-sulfur batteries. Small
2015;11:1488e511.
[7] Chen X, Xiao Z, Ning X, Liu Z, Yang Z, Zou C, Wang S, Chen X,
Chen Y, Huang S. Sulfur-impregnated, sandwich-type,
hybrid carbon nanosheets with hierarchical porous structure
for high-performance lithium-sulfur batteries. Adv Energy
Mater 2015;4. 13072-13072.
[8] Zhao MQ, Liu XF, Zhang Q, Tian GL, Huang JQ, Zhu W, Fei W.
Graphene/single-walled carbon nanotube hybrids: one-step
catalytic growth and applications for high-rate Li-S batteries.
ACS Nano 2012;6:10759e69.
[9] Niu S, Lv W, Zhang C, Shi Y, Zhao J, Li B, Yang Q-H, Kang F.
One-pot self-assembly of graphene/carbon nanotube/sulfur
hybrid with three dimensionally interconnected structure
for lithium-sulfur batteries. J Power Sources 2015;295:182e9.
[10] Sun Z, Zhang J, Yin L, Hu G, Fang R, Cheng H-M, Li F.
Conductive porous vanadium nitride/graphene composite as
chemical anchor of polysulfides for lithium-sulfur batteries.
Nat Commun 2017;8:14627.
[11] Li Z. MnO2egraphene nanosheets wrapped mesoporous
carbon/sulfur composite for lithium-sulfur batteries. Royal
Soc Open Sci 2018;5:171824.
[12] Yang X, Qian X, Jin L, Zhao D, Wang S, Rao D, Yao S, Shen X,
Zhou Y, Xi X. Mesoporous TiO2 nanosheet with a large
amount of exposed {001} facets as sulfur host for high-
performance lithium-sulfur batteries. J Solid State
Electrochem 2016;20:2161e8.
Please cite this article as: Jia Y et al., Sulfur encapsulated in nitrogen-doped graphene aerogel as a cathode material for high perfor-
mance lithium-sulfur batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.11.199
[13] Zhao C, Shen C, Xin F, Sun Z, Han W. Prussian blue-derived
Fe2O3/sulfur composite cathode for lithium-sulfur batteries.
Mater Lett 2014;137:52e5.
[14] Mahdavi H, Shahalizade T. Self-breathing ternary
nanocomposite based on nitrogen-doped graphene aerogel/
polyaniline/sulfur as a cathode material for lithium-sulfur
(Li-S) batteries. Ionics 2018;24:43e50.
[15] Huang L, Cheng J, Li X, Yuan D, Ni W, Qu G, Guan Q, Zhang Y,
Wang B. Sulfur quantum dots wrapped by conductive
polymer shell with internal void spaces for high-
performance lithium-sulfur batteries. J Mater Chem
2015;3:4049e57.
[16] Wei S, Ma L, Hendrickson KE, Tu Z, Archer LA. Metal-sulfur
battery cathodes based on PAN-sulfur composites. Am Chem
Soc 2015;137:12143e52.
[17] Wu R, Chen S, Deng J, Huang X, Song Y, Gan R, Wan X, Wei Z.
Hierarchically porous nitrogen-doped carbon as cathode for
lithium-sulfur batteries. J Energy Chem 2018;27:1661e7.
[18] Ma G, Wen Z, Jin J, Lu Y, Rui K, Wu X, Wu M, Zhang J.
Enhanced performance of lithium-sulfur battery with
polypyrrole warped mesoporous carbon/sulfur composite. J
Power Sources 2014;254:353e9.
[19] Xu J, Wu W, Guan L. Synthesis of 3D porous and
interconnected hollow carbon nanospheres array and its
applications in lithium-sulfur batteries. Chin Struct Chem
2017;36:1647e55.
[20] Chen R, Zhao T, Lu J, Wu F, Li L, Chen J, Tan G, Ye Y, Amine K.
Graphene-based three-dimensional hierarchical sandwich-
type architecture for high-performance Li/S batteries. Nano
Lett 2013;13:4642e9.
[21] Wang L, Zhao Y, Thomas ML, Byon HR. In situ synthesis of
bipyramidal sulfur with 3D carbon nanotube framework for
lithium-sulfur batteries. Adv Funct Mater 2014;24:2248e52.
[22] Tang C, Zhang Q, Zhao M, Huang J, Cheng X, Tian G, Peng H,
Wei F. Nitrogen-doped aligned carbon nanotube/graphene
sandwiches: facile catalytic growth on bifunctional natural
catalysts and their applications as scaffolds for high-rate
lithium-sulfur batteries. Adv Mater 2014;26:6100e5.
[23] Luo S, Yao M, Lei S, Yan P, Wei X, Wang X, Liu L, Niu Z.
Freestanding reduced graphene oxideesulfur composite
films for highly stable lithium-sulfur batteries. Nanoscale
2014;9:4646e51.
[24] Jiang Y, Lu M, Ling X, Jiao Z, Chen L, Chen L, Hu P, Zhao B.
One-step hydrothermal synthesis of three-dimensional
porous graphene aerogels/sulfur nanocrystals for lithium-
sulfur batteries. J Alloys Compd 2015;645:509e16.
[25] Li X, Guo G, Qin N, Deng Z, Lu Z, Shen D, Zhao X, Li Y, Sua B-L,
Wang H-E. SnS2/TiO2 nanohybrids chemically bonded on
nitrogen-doped graphene for lithium-sulfur batteries:
synergy of vacancy defects and heterostructure. Nanoscale
2018;10:15505e12.
[26] Li N, Gan F, Wang P, Chen K, Chen S, He X. In situ synthesis
of 3D sulfur-doped graphene/sulfur as a cathode material for
lithium-sulfur batteries. J Alloys Compd 2018;754:64e71.
[27] Walle MD, Zhang Z, Zhang M, You X, Li Y, Liu Y-N.
Hierarchical 3D nitrogen and phosphorous codoped
graphene/carbon nanotubesesulfur composite with
synergistic effect for high performance of lithium-sulfur
batteries. J Mater Sci 2018;53:2685e96.
[28] Chen J, Jia X, She Q, Wang C, Zhang Q, Zheng M, Dong Q. The
preparation of nano-sulfur/MWCNTs and its electrochemical
performance. Electrochim Acta 2010;55:8062e6.
[29] Xu Y, Sheng K, Li C, Shi G. Self-assembled graphene hydrogel
via a one-step hydrothermal process. ACS Nano
2010;4:4324e30.
[30] Zhang J, Shi Y, Ding Y, Peng L, Zhang W, Yu G. A conductive
molecular framework derived Li2S/N,P-codoped carbon
 international journal of hydrogen energy xxx (xxxx) xxx 11

cathode for advanced lithium-sulfur batteries. Adv Energy
Mater 2017;7:1602876.
[31] Wang M, Liang Q, Han J, Tao Y, Liu D, Zhang C, Lv W, Yang Q-
H. Catalyzing polysulfide conversion by g-C3N4 in a graphene
network for long-life lithium-sulfur batteries. Nano Res
2018;11:3480e9.
[32] Yang X, Wu D, Chen X, Fu R. Nitrogen-enriched nanocarbons
with a 3-D continuous mesopore structure from
polyacrylonitrile for supercapacitor application. J Phys Chem
C 2010;114:8581e6.
[33] Song J, Yu Z, Gordin ML, Wang D. Advanced sulfur cathode
enabled by highly crumpled nitrogen-doped graphene sheets
for high-energy-density lithium-sulfur batteries. Nano Lett
2015:5b03217.
[34] Geng X, Yi R, Yu Z, Zhao C, Li Y, Wei Q, Liu C, Zhao Y, Lu B,
Yang L. Isothermal sulfur condensation into carbon
nanotube/nitrogen-doped graphene composite for high
performance lithium-sulfur batteries. J Mater Sci Mater
Electron 2018;29:10071e81.
[35] Hummers WS, Offeman RE. Preparation of graphitic oxide. J
Am Chem Soc 1958;80:1339.
[36] Xu C, Wu Y, Zhao X, Wang X, Du G, Zhang J, Tu J. Sulfur/
three-dimensional graphene composite for high
performance lithium-sulfur batteries. J Power Sources
2015;275:22e5.
[37] Wang H, Zhang C, Liu Z, Wang L, Han P, Xu H, Zang K,
Dong S, Yao J, Cui G. Nitrogen-doped graphene nanosheets
with excellent lithium storage properties. J Mater Chem
2011;21:5430.
[38] Yan H, Cheng M, Zhong B, Chen Y. Three-dimensional
nitrogen-doped graphene/sulfur composite for lithium-
sulfur battery. Ionics 2016;22:1999e2006.
[39] Sun F, Wang J, Chen H, Li W, Qiao W, Long D, Ling L. High
efficiency immobilization of sulfur on nitrogen-enriched
mesoporous carbons for Li-S batteries. ACS Appl Mater
Interfaces 2013;5:5630e8.
[40] Zhao H, Peng Z, Wang W, Chen X, Fang J, Xu J. Reduced
graphene oxide with ultrahigh conductivity as carbon
coating layer for high performance sulfur@rgo cathode. J
Power Sources 2014;245:529e36.

Please cite this article as: Jia Y et al., Sulfur encapsulated in nitrogen-doped graphene aerogel as a cathode material for high perfor-
mance lithium-sulfur batteries, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.11.199