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Yolk@Shell Structured MnS@Nitrogen-Doped Carbon as a Sulfur

Host and Polysulfide Conversion Booster for Lithium/Sodium Sulfur
Batteries
Feng Ma,# Pei Hu,# Tanyuan Wang, Jiashun Liang, Rui Han, Jiantao Han, and Qing Li*
Cite This: ACS Appl. Energy Mater. 2021, 4, 3487−3494 Read Online

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ABSTRACT: Lithium-sulfur (Li-S) batteries have been regarded as an important

candidate for next-generation energy storage devices due to their low cost and high
theoretical energy density. However, several factors retard the practical use of Li-S
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batteries including the slow kinetics of lithium polysulfide (LiPS) transformation as

well as the shuttle effect induced by the diffusion of LiPS that damages the cycling
stability of Li-S batteries. In this study, a yolk@shell structured MnS@nitrogen-
doped carbon (MnS@N-C) is developed as the S host and polysulfide conversion
booster, which offers both the physical confinement of S species and accelerated
kinetics toward LiPS catalytic conversion. As a result, the developed S/yolk@shell
MnS@N-C delivers a higher rate performance compared to S/yolk@shell MnO@
N-C and S/N-C and long cycle life with a remaining capacity of 636.1 mAh g−1
after 330 cycles at 0.5C. When equipped with MnS@N-C functional separators, S/
yolk@shell MnS@N-C retains a capacity of 504.2 mAh g−1 after 1000 cycles at 1C.
In addition, S/yolk@shell MnS@N-C also delivers a decent capacity decay of
0.16% per cycle after 300 cycles at 0.5C in a room-temperature Na-S battery.
KEYWORDS: Li-S battery, MnS, yolk@shell structure, lithium polysulfide transformation, energy storage device

■ INTRODUCTION
Nowadays, the ever growing demands for renewable energy
such as solar energy, hydropower, and wind power call for
high-performance stationary energy storage systems with low
cost and long-term working stability.1,2 Meanwhile, emissions
from fossil fuel vehicles results in serious air pollutions and
climate changes, forcing people to develop advanced energy
storage systems with high energy and power outputs.3,4 With
this regard, lithium-sulfur (Li-S) batteries with high theoretical
energy density and naturally abundant sources5−8 have
received much attention as promising energy storage devices.
With those significances, Li-S batteries also have some
drawbacks. The low conductivity of S (5 × 10−30 S cm−1)
hinders the full utilization of S and leads to a low capacity of
the Li-S battery.8−10 In parallel, Li polysulfides (LiPSs) such as
Li2S8, Li2S6, and Li2S4, which are the discharge intermediates of
S, are highly soluble in organic electrolytes. They can easily
diffuse away from the electrode and lead to the loss of active
material and shuttle effect. For this reason, the cycling stability
of Li-S batteries is relatively worse than that of commercial
lithium-ion batteries. In addition, the sluggish LiPS conversion
kinetics and the random deposition of Li2S retard the capacity
retention when working at high current densities.
Several approaches have been employed to solve those
problems. Conductive carbons, such as ordered mesoporous
carbons,11 carbon nanotubes,12,13 graphenes,14 hollow carbon
spheres,15,16 have been utilized to improve the conductivity of
S and enhance S utilization. However, nonpolar carbons
exhibit limited affinity with polar LiPS, resulting in severe
capacity decay in long-term cycling.17 To further improve the
electrochemical performance of Li-S batteries, doping carbon
with heteroatoms, such as nitrogen,18,19 boron,20,21 and
phosphorus,22 is regarded as an effective method to restrict
the severe diffusion of LiPS. The polar heteroatoms provide
carbon materials with more defects and active sites for LiPS
anchoring. Meanwhile, some polar materials such as transition
metal oxides,17,23,24 sulfides,25−28 nitrides,29 and phosphides,30
have been designed to improve the affinity of neat carbon for
LiPS entrapment due to their strong chemical interaction with
LiPS. Recently, MnO2 has been reported as Li-S battery
cathodes with reasonable stability due to the efficient
entrapment and conversion of LiPS.31−33 Considering the
higher electroconductivity and more sulfiphilic property of Mn
sulfides than the oxides,9,34,35 MnSx is potentially applicable in
Received: December 27, 2020
Accepted: March 18, 2021
Published: March 30, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acsaem.0c03235

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Li-S batteries when combined with porous and conductive

carbon substrates.
In this study, a yolk@shell structured MnS@nitrogen-doped
carbon (MnS@N-C) was developed and employed as both the
efficient S host and LiPS conversion promoter. The fabrication
of such a yolk@shell nanocomposite enables combining the
advantages of physical confinement and catalytical conversion
of LiPS. N-C with a high conductivity as well as high surface
area endows highways for electron conducting and physical
confinement of the S species. The cavity of yolk@shell MnS@
N-C provides enough space for S confinement, and MnS
exhibits strong chemical binding with LiPS and effective
catalytic activity toward LiPS transformation. These advantages
improve the redox kinetics of LiPS conversion and alleviate
LiPS leakage, ensuring better rate capability and cycling
stability compared with yolk@shell MnO@N-C, core@shell
MnS@N-C, and N-C in Li-S batteries. Therefore, the S/yolk@
shell MnS@N-C electrode delivers a high capacity as well as
excellent rate performance with capacities of 1247.5 mAh g−1
at 0.1C and 390.1 mAh g−1 at 4C. Meanwhile, it also exhibits
stable cycling stability with a high capacity retention of 75%
after 330 cycles at 0.5C. When equipped with a functional Figure 2. (a) XRD patterns of yolk@shell MnS@N-C, core@shell
separator coated with yolk@shell MnS@N-C, the electrode MnS@N-C, and N-C. (b−d) SEM, TEM, and HRTEM images of
exhibits a capacity of 504.2 mAh g−1 after 1000 cycles at 1C. In yolk@shell MnS@N-C, respectively. (e−i) High-angle annular dark
addition, S/yolk@shell MnS@N-C is also employed as the field (HADDF) image of yolk@shell MnS@N-C and the correspond-
cathode of room-temperature sodium sulfur (Na-S) batteries ing elemental mapping of Mn, S, N, and C.
and delivers a high initial capacity of 893.9 mAh g−1 at 0.1C
and excellent cycling stability at 0.5C for 300 cycles with a with the cubic Fm3m α-MnS phase (JCPDS 06-0518). The
capacity decay of 0.16% per cycle.

■
RESULTS AND DISCUSSION
Figure 1 displays the process of synthesizing yolk@shell
MnS@N-C. The MnCO3 precursor was first coated with
Figure 1. Scheme illustration of the preparation of yolk@shell MnS@
N-C.
polydopamine (PDA) and then reacted with S at high
temperature (700 °C) to yield core@shell structured MnS@
N-C. Here, PDA acts as the nitrogen and carbon sources for
preparing N-C. The possible reaction mechanism is displayed
in eqs 1−3. Finally, yolk@shell MnS@N-C was obtained by
etching the excessive MnS in HCl solution, as shown in eq 4.
For comparison, yolk@shell MnO@N-C was also prepared
with a similar approach (See the Experimental Section).
MnCO3 → MnO + CO2 (g)
MnO + S + H 2 → MnS + H 2O (g)
MnO + S + C → MnS + CO (g)
MnS + 2HCl → MnCl 2 + H 2S (g)
The crystal phases of core@shell MnS@N-C, yolk@shell
MnS@N-C, and N-C hollow spheres are measured by the X-
ray diffraction (XRD) test (Figure 2a). Both the XRD patterns
of core@shell MnS@N-C and yolk@shell MnS@N-C match
intensity of MnS peaks of yolk@shell MnS@N-C turns weaker
due to the reduced amount of MnS after acid etching. The
characteristic diffraction peaks at 29.6°, 34.3°, 49.2°, 61.3°,
72.2°, and 82.5° can be indexed to the (111), (200), (220),
(222), (400), and (420) facets of α-MnS. A slight left shift of
the peaks of yolk@shell MnS@N-C may result from the
etching-derived defects in α-MnS crystals, which lead to the
expansion of the lattice spacings. As for N-C, no peaks related
to α-MnS can be observed in the XRD pattern, revealing that
MnS has been completely removed.
The spherical morphology of yolk@shell MnS@N-C and
core@shell MnS@N-C with an average diameter of 1 μm can
be observed in the scanning electron microscopy (SEM)
images (Figure 2b and Figures S1 and S2). The large cavity
between the carbon shell and MnS core can be observed from
a broken yolk@shell MnS@N-C sphere. The MnS content in
yolk@shell MnS@N-C is measured to be 32 wt % by the TGA
(thermal gravity analysis) measurement (Figure S3). The
cavity created by the selective etching of MnS provides a
higher surface area of yolk@shell MnS@N-C (91.12 m2 g−1)
than core@shell MnS@N-C (2.11 m2 g−1) (Figures S4 and
S5) and abundant space for S confinement. The large cavity
between the core and carbon shell with a thickness of ca. 30
nm can also be clearly observed in the transmission electron
(1) microscopy (TEM) image (Figure 2c). The elemental
mapping images (Figure 2f−i) show a uniform distribution
(2) of Mn and S in the core area and confirm that MnS is
encapsulated in the N-C shell. From the high-resolution TEM
(3) (Figure 2d) image, the lattice spacing of MnS is measured to
be 2.62 Å, which is very close to the standard value of the
(4)
(200) facet of MnS (2.61 Å) and in accordance with the XRD
result.
The typical XRD patterns (Figure S6) of rhombic S (JCPDS
08-0247) and the sphere morphologies (Figures S7 and S8) of
S/yolk@shell MnS@N-C and S/N-C indicate the successful
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confinement of S in the pore and cavity of yolk@shell MnS@
N-C and N-C. However, S aggregates into large bulks in the S/
core@shell MnS@N-C sample (Figure S9) due to the low
surface area, which fails to accommodate large amounts of S.
TGA measurement indicates that the S contents of S/yolk@
shell MnS@N-C and S/N-C to be 68 wt % (Figure S10).
To study the role of MnS and N-C in LiPS entrapment,
yolk@shell MnS@N-C, yolk@shell MnO@N-C, and N-C
were subjected to a LiPS adsorption measurement. The
ultraviolet−visible (UV−Vis) spectra of the Li2S4 solution
treated by the adsorption of the studied samples show that
yolk@shell MnS@N-C delivers stronger capability than yolk@
shell MnO@N-C and N-C sphere for LiPS entrapment (Figure
3a). The original Li2S4 solution turned colorless after
Figure 3. (a) UV−Vis spectra of pristine Li2S4 solution and the
solution after with the adsorption treatment of yolk@shell MnS@N-C
and N-C. High-resolution (b) Mn 2p and (c) S 2p X-ray
photoelectron spectra of yolk@shell MnS@N-C before and after
Li2S4 interaction. (d) CV curves of yolk@shell MnS@N-C/Li and N-
C/Li asymmetric cells with 0.1 M Li2S8 as a catholyte at a scan rate of
1 mV s−1.
immersion with yolk@shell MnS@N-C while the color of N-
C-immersed solution cannot be fully faded (Figure S11).
These results show that MnS in yolk@shell MnS@N-C
provides additional LiPS trapping sites to N-C. Meanwhile, it
demonstrates the importance of MnS in this study as MnS
exhibits superior LiPS adsorption capability to MnO.
The interaction of LiPS with MnS was confirmed by X-ray
photoelectron spectroscopy (XPS) measurement. As shown,
for the initial yolk@shell MnS@N-C, a pair of spin−orbit
double peaks of Mn 2p3/2 and Mn 2p1/2 are presented at 642.2
and 654.2 eV, which refer to the Mn(II)−S bond (Figure
3b).36,37 The peak at 646.7 eV may result from the Mn−O
bond due to the slight oxidation in air, which has been also
observed in other studies.34 After the adsorption of Li2S4, the
positions of Mn 2p3/2 and Mn 2p1/2 peaks remain unchanged
while the intensity of the Mn−O component decreases,
suggesting the newly formed Mn−S bond after the interaction
of LiPS. The S 2p spectra of yolk@shell MnS@N-C consist of
three pairs of peaks at 162.1/162.4, 162.8/163.6, and 166.8/
167.2 eV corresponding to S−Mn, S−S, and S−O bonds
(Figure 3c).34 The S−O bond may be the result of the slight
oxidation of S. After interacting with LiPS, the component of
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S−Mn increases while the S−O component decreases. The
increased amount of S−Mn component is attributed to the
interaction with LiPS, which provides additional S and reduces
oxygen species. As for the N 1s spectra of yolk@shell MnS@N-
C (Figure S12a), the peaks at 398.2, 398.9, and 400.7 eV are
assigned to pyridinic, pyrrolic, and graphitic nitrogen.38−40 The
N content of yolk@shell MnS@N-C is measured to be 1.82 at
% (Table S1). After interacting with Li2S4 (Figure S12b), the
three peaks of N 1s spectrum exhibit a minor negative shift
(∼0.1 eV), likely induced by the shielding effect of Li.39,41 It
can be concluded that MnS plays a key role in the LiPS
entrapment and has a strong chemical binding with LiPS,
which may provide a fast LiPS redox kinetics and efficient
confinement of LiPS.
The performance of MnS in LiPS conversion was further
studied by the electrochemical measurement. Yolk@shell
MnS@N-C, yolk@shell MnO@N-C, and N-C electrodes
were employed to construct an asymmetric cell with 0.1 M
Li2S8 as a catholyte and lithium foil as a reference electrode.
The cyclic voltammetry (CV) curve of yolk@shell MnS@N-C
asymmetric cells delivers two catholic peaks and an anodic
peak (Figure 3d). In the cathodic process, yolk@shell MnS@
N-C shows a higher onset potential of 2.40 V than yolk@shell
MnO@N-C (2.37 V) and N-C (2.34 V), representing the
highest intrinsic activity in LiPS reduction. The cathodic peaks
at the positions of 2.26 and 1.91 V correspond to the Li2S8/
Li2S4 and Li2S4/Li2S conversion, respectively. For comparison,
yolk@shell MnO@N-C shows lower current, especially in the
Li2S4/Li2S transformation process. As for N-C, it shows only
one catholic peak at 2.17 V, indicating a large polarization in
LiPS conversion. The Li2S4 to Li2S transformation (Li2S
deposition) kinetics of the electrodes can be directly measured
by a potentiostatic test. The yolk@shell MnS@N-C and N-C
asymmetric batteries were discharged to 2.05 V in a Li2S8
catholyte followed by a chronoamperometry test at a constant
voltage of 2.05 V. The test can clearly demonstrate the catalytic
activity of yolk@shell MnS@N-C for the conversion of LiPS to
Li2S. As shown in Figure S13, the yolk@shell MnS@N-C
electrode exhibits a higher integrated capacity (243.2 mAh
g−1) of Li2S deposition than N-C (182.1 mAh g−1). The higher
capacity of yolk@shell MnS@N-C represents that more
amount of LiPS can be transformed to Li2S under the same
bias potential applied, demonstrating the propelled LiPS
catalytic conversion on yolk@shell MnS@N-C.
The anodic peak of the CV curve (Figure 3d) at 2.50 V
refers to the decomposition of Li2S and the conversion of
short-chain Li2Sx (2 ≤ x < 4) to long-chain Li2Sy (4 < y ≤
8).42,43 In the oxidation process, a superior activity of yolk@
shell MnS@N-C for Li2S decomposition can be achieved with
an onset potential of 2.17 V, which is lower than those of
yolk@shell MnO@N-C (2.20 V) and N-C (2.21 V). This
result demonstrates that yolk@shell MnS@N-C can deliver not
only stronger chemical interaction with LiPS but also higher
electrocatalytic activity in LiPS transformation compared with
yolk@shell MnO@N-C and N-C. The higher activity of yolk@
shell MnS@N-C may stem from the strong interactions of
MnS with LiPS, which optimizes the adsorption/desorption of
LiPS and provides internal mediator to propel the LiPS redox
reaction as studied before in the cases of transition metal
oxide/sulfide.24,25,44
S/yolk@shell MnS@N-C, S/yolk@shell MnO@N-C, and
S/N-C were employed as the cathodes of Li-S batteries and
subjected to discharge and charge tests under certain current
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Figure 4. (a) Rate performance of S/yolk@shell MnS@N-C and S/N-C. (b−d) Charge/discharge curves of S/yolk@shell MnS@N-C, S/yolk@
shell MnO@N-C, and S/N-C, respectively. (e) Long-term cycling performance of S/yolk@shell MnS@N-C, S/yolk@shell MnO@N-C, and S/N-
C.
densities. S/core@shell MnS@N-C was used as the control
sample to study the effect of morphology on the electro-
chemical performance of yolk@shell MnS@N-C. The S/yolk@
shell MnS@N-C electrode exhibits a capacity of 1247.5 mAh
g−1 initially at 0.1C, which is higher than S/yolk@shell MnO@
N-C (1137.3 mAh g−1) and S/N-C (1162.1 mAh g−1) (Figure
4a). This capacity of S/yolk@shell MnS@N-C refers to a
specific energy of 2744.5 Wh kg−1 based on S. At the
subsequent cycles under various current densities, S/yolk@
shell MnS@N-C shows the capacities of 1061.2, 813.0, and
662.7 mAh g−1 at 0.2C, 0.5C, and 1C. Even at 4C, it still
retains a capacity of 390.1 mAh g−1, indicating an excellent rate
capability and a fast LiPS conversion kinetics. When the
current density comes back to 0.2C, it still reversibly retains a
capacity of 959.1 mAh g−1, suggesting a high stability of the S/
yolk@shell MnS@N-C electrode. For comparison, S/yolk@
shell MnO@N-C and S/N-C deliver capacities of 943.6 and
836.5 mAh g−1 at 0.2C and 671.0 and 613.8 mAh g−1 at 0.5C,
respectively, remarkably lower than S/yolk@shell MnS@N-C.
As for S/core@shell MnS@N-C, it exhibits an initial capacity
of 1091.4 mAh g−1 at 0.1C. However, the rate capability is
rather poor as it delivers a capacity of 174.5 mAh g−1 at a 1C
rate and the capacity quickly decreases in the prolonged
cycling process (Figure S14). This may be caused by the very
limited surface area of core@shell MnS@N-C, which fails to
incorporate S in the pores. As a result, S/core@shell MnS@N-
C exhibits very low kinetics in LiPS conversion and poor
stability. The control sample proves that the yolk@shell
morphology of yolk@shell MnS@N-C is also critical in the
performance of Li-S batteries.
The discharge/charge profiles of S/yolk@shell MnS@N-C,
S/yolk@shell MnO@N-C, and S/N-C are shown in Figure
4b−d. Under a current density of 0.1C, the discharge curve of
S/yolk@shell MnS@N-C is composed of two plateaus at 2.32
and 2.11 V, which contribute the capacities of 392.0 and 855.5
mAh g−1, respectively. The former short plateau is assigned to
the S8/Li2S4 reduction reaction,31 and the long plateau
represents the further Li2S4/Li2S conversion process. In the
oxidation process, the long plateau between a voltage range of
2.2−2.34 V is ascribed to the reversible delithiation of Li2S2/
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Li2S to short-chain LiPS.45 The plateaus in the charge/
discharge curves of S/yolk@shell MnS@N-C are in accordance
with the redox peaks in the CV plots (Figure S15). Even under
a higher current density of 3C, S/yolk@shell MnS@N-C can
still maintain the two-plateau shape. As for S/yolk@shell
MnO@N-C and S/N-C, they have the same shape of
discharge/charge profile at 0.1C but the second plateaus of
the discharge profiles disappear under higher current densities,
revealing the sluggish kinetics in Li2S4/Li2S conversion.
The LiPS transformation kinetics of the electrodes is also
confirmed by electrochemical impedance spectroscopy (EIS)
analysis of S/yolk@shell MnS@N-C and other electrodes after
the rate performance test (Figure S16). The EIS plots consist
of two compressed arcs in the middle frequency region and a
declining line in the low frequency area. The former
compressed arc represents the charge transfer resistance
(Rct), while the latter results from the passivation layer of S
species.23,46 The smaller Rct of the S/yolk@shell MnS@N-C
electrode than S/yolk@shell MnO@N-C and S/N-C electro-
des confirms the faster LiPS conversion kinetics. Meanwhile, it
also suggests that MnS may exhibit better intrinsic activity due
to its more sulfiphilic property.9,35 The smallest resistance of
the passivation layer of S/yolk@shell MnS@N-C indicates that
yolk@shell MnS@N-C exhibits the most effective entrapment
on LiPS, which avoids the migration of LiPS from the cathode
side to Li metal. Owing to the effective entrapment of yolk@
shell MnS@N-C, the accumulation of S species was alleviated,
which favors the long-term cycling stability.
The cycling stabilities of S/yolk@shell MnS@N-C and other
electrodes are first evaluated by the discharge/charge cycling at
a rate of 0.1C (Figure S17). S/yolk@shell MnS@N-C holds a
capacity retention of 91.3%, higher than those of S/yolk@shell
MnO@N-C (86.1%) and S/N-C (84.2%). For the prolonged
cycling at 0.5C (Figure 4e), S/yolk@shell MnS@N-C delivers
an initial capacity of 848.4 mAh g−1. After 330 cycles, it still
retains 636.1 mAh g−1, corresponding to a capacity decay of
0.075% per cycle, and the Coulombic efficiency in the cycling
process is higher than 99%. This cycling stability is much better
than those of the previous studies with MnS as a LiPS
immobilizer.28,34 S/yolk@shell MnO@N-C exhibits a capacity
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Figure 5. Electrochemical performance of S/yolk@shell MnS@N-C as the cathode of a Na-S battery: (a) discharge/charge profile at 0.1C; (b) rate
performance; and (c) long-term cycling performance at 0.5C.
of 476.9 mAh g−1 after 330 cycles, yielding a capacity decay of
0.11% per cycle. In contrast, S/N-C exhibits a capacity of only
709.1 mAh g−1 initially and the capacity decreases very fast in
the following 150 cycles. Finally, S/N-C shows a capacity of
only 146.9 mAh g−1 after 330 cycles, corresponding to a
capacity decay as high as 0.24% per cycle. The improved
cycling stability of S/yolk@shell MnS@N-C is attributed to
the strong anchoring effect of MnS on LiPS and the excellent
LiPS transformation electrocatalytic activity that not only
improves the electrochemical kinetics but also alleviates the
LiPS accumulation and shuttle effect.
Given that there is still a small amount of LiPS that leaked
out of the cathode, which may further migrates to the anode
side, it is still challenging for the Li-S battery to maintain the
long-term stability (e.g., 1000 cycles). Recently, several
research efforts have been taken to place a LiPS barrier
between the cathode and anode, which can endow additional
sites to adsorb S species and suppress the shuttle effect.47 In
this study, the electrochemical performance of the S/yolk@
shell MnS@N-C electrode can be further improved by the
functional separator with yolk@shell MnS@N-C coated. With
the functional separator, the S/yolk@shell MnS@N-C
electrode delivers an initial capacity of 1522.0 mAh g−1 at
0.1C, which corresponds to a high S utilization of 91%. It also
shows excellent rate capability with capacities of 1010.1, 920.2,
777.1, and 551.0 mAh g−1 at 0.5C, 1C, 2C, and 5C rates
(Figure S18a,b). The long-term stability of S/yolk@shell
MnS@N-C with the functional separator was evaluated by
cycling at 1C (Figure S18c). After cycling for 1000 cycles, S/
yolk@shell MnS@N-C still retains a capacity of 504.2 mAh
g−1, which corresponds to a specific energy of 1058.8 Wh kg−1
and a very low capacity decay of 0.049% per cycle due to the
assistance of the dual protection of yolk@shell MnS@N-C.
Inspired by the excellent performance of S/yolk@shell
MnS@N-C in Li-S batteries, S/yolk@shell MnS@N-C was
also employed as a cathode material for room-temperature Na-
S batteries, which have a lower cost than Li-S batteries but
suffer from the more sluggish kinetics and demand effective
sodium polysulfide transformation.48,49 The initial discharge
capacity at 0.1C is 893.9 mAh g−1 in a range of 1.2−2.8 V,
indicating that about 53% of S in S/yolk@shell MnS@N-C is
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utilized (Figure 5a). The rate performance of the S/yolk@shell
MnS@N-C electrode in Na-S batteries is shown in Figure 5b.
Even at a 1C rate, S/yolk@shell MnS@N-C still shows a
capacity of 299.0 mAh g−1. When cycling at a 0.5C rate, S/
yolk@shell MnS@N-C retains a capacity of 213.1 mAh g−1
after 300 cycles, corresponding to a capacity decay of 0.16%
per cycle (Figure 5c). Considering the high S content of S/
yolk@shell MnS@N-C and high cutoff voltage of discharge
(1.2 V), this electrochemical performance is comparable to
many previous works.50−52 In comparison, the S/N-C
electrode only delivers a capacity of 53.8 mAh g−1 at 0.5C
after 150 cycles and suffers from severe overcharge derived
from the shuttle effect (Figure S19). The enhanced rate and
cycling performance may result from the excellent catalytic
activity in polysulfide conversion that increases the S utilization
and alleviate the bad effect of sodium polysulfide. The detailed
mechanism of sodium polysulfide conversion propelled by
MnS requires further studies in the following works.
■ CONCLUSIONS
In this work, a yolk@shell structured MnS@N-C was prepared
and employed as the S host and polysulfide conversion booster
for Li-S and Na-S batteries. Yolk@shell MnS@N-C exhibits
the strong chemical adsorption capability of LiPS and excellent
catalytic activity in LiPS redox conversion, which not only
improves the LiPS redox kinetics but also alleviates the LiPS
accumulation during cycles. Therefore, S/yolk@shell MnS@N-
C displays the high initial capacity and good rate performance
with capacities of 1247.5 mAh g−1 at 0.1C and 390.1 mAh g−1
at 4C. In the long cycling, it retains a capacity of 636.1 mAh
g−1, corresponding to a capacity decay of 0.075% per cycle.
The cycling stability can be further improved with a yolk@shell
MnS@N-C functional separator, which brings about a capacity
of 504.2 mAh g−1 after 1000 cycles at 1C. In addition, the
performance of S/yolk@shell MnS@N-C in room-temperature
Na-S batteries was also discussed. This study provides an easy
and novel route to prepare yolk@shell structured materials for
the high energy density and long cycling life energy storage
systems.
https://doi.org/10.1021/acsaem.0c03235
ACS Appl. Energy Mater. 2021, 4, 3487−3494
ACS Applied Energy Materials
■
EXPERIMENTAL SECTION
Preparation of Core@Shell MnS@N-C, Yolk@Shell MnS@N-
C, and Yolk@Shell MnO@N-C. A spherical MnCO3 was used as a
precursor prepared by a carbonate precipitation method. Briefly, 20
mmol of MnSO4 was dissolved in 400 mL of deionized water and 80
mL of ethanol mixed solution with a stirring speed of 600 rpm to
which 200 mmol of NH4HCO3 dissolved in 400 mL of deionized
water was added. To the obtained MnCO3 suspension were added 1 g
of dopamine hydrochloride and three drops of concentrated ammonia
solution (25 wt %) in sequence to yield core@shell MnCO3@
polydopamine (MnCO3@PDA). MnCO3@PDA was mixed with
sublimed S with a mass ratio of 1:1, subjected to a tube furnace, and
annealed at 700 °C for 3 h under a flowing H2/Ar (5% H2)
atmosphere to obtain core@shell MnS@N-C.
Finally, yolk@shell MnS@N-C was obtained by etching core@shell
MnS@N-C in 0.5 M HCl for 3 h at room temperature.
Yolk@shell MnO@N-C was prepared by a similar method to
yolk@shell MnS@N-C except that MnCO3@PDA was directly
subjected to the thermal treatment without adding S.
Preparation of Hollow N-C Spheres. N-C was prepared by a
similar approach to yolk@shell MnS@N-C except that the etching
condition is immersion of core@shell MnS@N-C in 1 M HCl for 24
h.
Preparation of S Composites (S/Yolk@Shell MnS@N-C, S/
Yolk@Shell MnO@N-C, S/Core@Shell MnS@N-C, and S/N-C).
The preparation of the S composites was based on an approach
reported before.42,43
■
MATERIAL CHARACTERIZATIONS
The X-ray diffraction (XRD) tests performed on a PANalytical
B.V. diffractometer with a Cu Kα radiation source were
employed to determine the crystal structure of the samples.
The scanning electron microscopy (SEM, Nova NanoSEM
450, 10 kV) and transmission electron microscopy (TEM,
Tecnai G2 F30, 200 kV) measurements were performed to
evaluate the morphology and structure of the samples. The S
content was confirmed using a thermogravimetric analyzer
(PerkinElmer, TGA8000) under flowing N2. The surface areas
and pore volumes of the samples were obtained by a
Brunauer−Emmett−Teller (BET) method with a surface
area analyzer (Micromeritics, ASAP2020). The electronic
structures of the samples were measured by X-ray photo-
electron spectroscopy (XPS) with an X-ray photoelectron
spectrometer (AXIS-ULTRA DLD-600 W). The MnS@N-C
sample was subjected to a ball-milling treatment before the
XPS measurement. The adsorption measurement of LiPS was
performed using an ultraviolet−visible (UV−Vis) analyzer
(Shimadzu, SolidSpec-3700).
Electrochemical Measurements. The electrodes were
prepared by a common approach reported before.42,43 The
electrodes were integrated in CR2016 coin cells with lithium
foil as the anode and Celgard 2500 membrane as the
separators. Lithium bis(trifluoromethanesulfonyl)imide (LiTF-
SI, 1 M) in DME/DOL (1/1 V/V) solution with 2 wt %
LiNO3 as additives was used as the electrolyte. The
electrolyte/sulfur ratio of each cell was controlled to be 20.
The discharge/charge measurement was performed with a
LAND tester (CT2001A) in a voltage range of 1.7−2.8 V.
For Na-S batteries, the preparation of the cathode (S/yolk@
shell MnS@N-C or S/N-C) is the same as that for Li-S
batteries. The Na-S coin cell was assembled with sodium foil as
an anode and 1 M NaCF3SO3 in diethylene glycol dimethyl
ether (G2) as an electrolyte. The electrochemical window was
controlled in a range of 1.2−2.8 V for the galvanic discharge/
charge test.
3492
www.acsaem.org Article
The cyclic voltammetry (CV) plots were measured using an
electrochemical workstation (CHI760E). For the Li-S battery,
the scan rate was set to 0.1 mV s−1.
To evaluate the electrocatalytic performance of the samples,
the electrodes were assembled in asymmetric cells for CV and
Li2S deposition measurements as reported before.42,43 The
lithium foils were employed as reference and counter
electrodes. The electrolyte used in this measurement was a
Li2S8-contaning catholyte (1 M LiTFSI + 0.1 M Li2S8 in
DME/DOL). The preparation of the working electrode was
given briefly in the following. The material (yolk@shell MnS@
N-C, yolk@shell MnO@N-C, or N-C) was mixed with carbon
black and sodium alginate with a mass ratio of 4:1:1, and the
obtained uniform slurry was casted onto carbon paper to form
an electrode.
■
ASSOCIATED CONTENT
* Supporting Information
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acsaem.0c03235.
SEM and TEM images of yolk@shell MnS@N-C, core@
shell MnS@N-C, S/yolk@shell MnS@N-C, and S/
core@shell MnS@N-C; N2 adsorption/desorption
curves and BET surface areas of yolk@shell MnS@N-
C, core@shell MnS@N-C, and N-C; TGA curves of S/
yolk@shell MnS@N-C and S/N-C; XPS of N 1s before
and after Li2S4 adsorption; electrochemical performance
of S/core@shell MnS@N-C; EIS plots of S/yolk@shell
MnS@N-C, S/yolk@shell MnO@N-C, and S/N-C;
electrochemical performance of S/yolk@shell MnS@
N-C with a yolk@shell MnS@N-C functional separator;
and cycling performance of S/N-C in the room-
temperature Na-S battery (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Qing Li − State Key Laboratory of Material Processing and
Die & Mould Technology, School of Materials Science and
Engineering, Huazhong University of Science and Technology,
Wuhan, Hubei 430074, China; Shenzhen Institute of
Huazhong University of Science and Technology, Shenzhen
518000, China; orcid.org/0000-0003-4807-030X;
Email: qing_li@hust.edu.cn
Authors
Feng Ma − State Key Laboratory of Material Processing and
Die & Mould Technology, School of Materials Science and
Engineering, Huazhong University of Science and Technology,
Wuhan, Hubei 430074, China; Shenzhen Institute of
Huazhong University of Science and Technology, Shenzhen
518000, China; orcid.org/0000-0002-0856-2783
Pei Hu − State Key Laboratory of Material Processing and Die
& Mould Technology, School of Materials Science and
Engineering, Huazhong University of Science and Technology,
Wuhan, Hubei 430074, China
Tanyuan Wang − State Key Laboratory of Material Processing
and Die & Mould Technology, School of Materials Science
and Engineering, Huazhong University of Science and
Technology, Wuhan, Hubei 430074, China; Shenzhen
Institute of Huazhong University of Science and Technology,
Shenzhen 518000, China
https://doi.org/10.1021/acsaem.0c03235
ACS Appl. Energy Mater. 2021, 4, 3487−3494
ACS Applied Energy Materials
Jiashun Liang − State Key Laboratory of Material Processing
and Die & Mould Technology, School of Materials Science
and Engineering, Huazhong University of Science and
Technology, Wuhan, Hubei 430074, China
Rui Han − State Key Laboratory of Material Processing and
Die & Mould Technology, School of Materials Science and
Engineering, Huazhong University of Science and Technology,
Wuhan, Hubei 430074, China
Jiantao Han − State Key Laboratory of Material Processing
and Die & Mould Technology, School of Materials Science
and Engineering, Huazhong University of Science and
Technology, Wuhan, Hubei 430074, China; orcid.org/
0000-0002-9509-3785
Complete contact information is available at:
https://pubs.acs.org/10.1021/acsaem.0c03235
Author Contributions
#
F.M. and P.H. contributed equally.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was financially supported by the National Materials
Genome Project (2016YFB0700600), National Nature Science
Foundation of China (21972051), and Science, Technology
and Innovation Commission of Shenzhen Municipality
(JCYJ20180305180918034). The authors thank the Analytical
and Testing Center of Huazhong University of Science and
Technology (HUST) for carrying out the XRD, XPS, SEM,
TEM, and TGA measurements.
■
REFERENCES
(1) Lei, J.; Liu, T.; Chen, J. J.; Zheng, M.; Zhang, Q.; Mao, B.; Dong,
Q. Exploring and Understanding the Roles of Li2Sn and the Strategies
to beyond Present Li-S Batteries. Chem 2020, 6, 2533−2557.
(2) Tian, Y.; Zeng, G.; Rutt, A.; Shi, T.; Kim, H.; Wang, J.; Koettgen,
J.; Sun, Y.; Ouyang, B.; Chen, T.; Lun, Z.; Rong, Z.; Persson, K.;
Ceder, G. Promises and Challenges of Next-Generation “Beyond Li-
ion” Batteries for Electric Vehicles and Grid Decarbonization. Chem.
Rev. 2020, 1623.
(3) Huang, M.; Li, M.; Niu, C.; Li, Q.; Mai, L. Recent Advances in
Rational Electrode Designs for High-Performance Alkaline Recharge-
able Batteries. Adv. Funct. Mater. 2019, 29, 1807847.
(4) Ma, F.; Li, Q.; Wang, T.; Zhang, H.; Wu, G. Energy storage
materials derived from Prussian blue analogues. Sci. Bull. 2017, 62,
358−368.
(5) Xie, J.; Song, Y. W.; Li, B. Q.; Peng, H. J.; Huang, J. Q.; Zhang,
Q. Direct Intermediate Regulation Enabled by Sulfur Containers in
Working Lithium-Sulfur Batteries. Angew. Chem., Int. Ed. 2020, 59,
22150−22155.
(6) He, J.; Bhargav, A.; Manthiram, A. Molybdenum Boride as an
Efficient Catalyst for Polysulfide Redox to Enable High-Energy-
Density Lithium-Sulfur Batteries. Adv. Mater. 2020, 32, 2004741.
(7) Liang, Z.; Yang, D.; Tang, P.; Zhang, C.; Jacas Biendicho, J.;
Zhang, Y.; Llorca, J.; Wang, X.; Li, J.; Heggen, M.; David, J.; Dunin-
Borkowski, R. E.; Zhou, Y.; Morante, J. R.; Cabot, A.; Arbiol, J.
Atomically Dispersed Fe in a C2N Based Catalyst as a Sulfur Host for
Efficient Lithium−Sulfur Batteries. Adv. Energy Mater. 2020, 11,
2003507.
(8) Seh, Z. W.; Sun, Y.; Zhang, Q.; Cui, Y. Designing High-Energy
Lithium-Sulfur Batteries. Chem. Soc. Rev. 2016, 45, 5605−5634.
(9) Wang, X.; Zhao, X.; Ma, C.; Yang, Z.; Chen, G.; Wang, L.; Yue,
H.; Zhang, D.; Sun, Z. Electrospun Carbon Nanofibers with MnS
Sulfiphilic Sites as Efficient Polysulfide Barriers for High-Performance
3493
www.acsaem.org Article
Wide-Temperature-Range Li−S Batteries. J. Mater. Chem. A 2020, 8,
1212−1220.
(10) Guo, D.; Qian, X.; Jin, L.; Yao, S.; Shen, X.; Li, T.; Qin, S.
Graphene Oxide Coated Nanosheet-Like γ-MnS@KB-S Fabricated by
Spray Drying for High Energy Density Li-S Batteries. Int. J. Energy Res.
2020, 44, 11274−11287.
(11) Ji, X.; Lee, K. T.; Nazar, L. F. A Highly Ordered
Nanostructured Carbon-Sulphur Cathode for Lithium-Sulphur
Batteries. Nat. Mater. 2009, 8, 500−506.
(12) Zhao, Y.; Wu, W.; Li, J.; Xu, Z.; Guan, L. Encapsulating
MWNTs into Hollow Porous Carbon Nanotubes: A Tube-in-Tube
Carbon Nanostructure for High-Performance Lithium-Sulfur Bat-
teries. Adv. Mater. 2014, 26, 5113−5118.
(13) Cheng, X. B.; Huang, J. Q.; Zhang, Q.; Peng, H. J.; Zhao, M.
Q.; Wei, F. Aligned Carbon Nanotube/Sulfur Composite Cathodes
with High Sulfur Content for Lithium-Sulfur Batteries. Nano Energy
2014, 4, 65−72.
(14) Cao, J.; Chen, C.; Zhao, Q.; Zhang, N.; Lu, Q.; Wang, X.; Niu,
Z.; Chen, J. A Flexible Nanostructured Paper of a Reduced Graphene
Oxide-Sulfur Composite for High- Performance Lithium-Sulfur
Batteries with Unconventional Configurations. Adv. Mater. 2016,
28, 9629−9636.
(15) Nersisyan, H. H.; Joo, S. H.; Yoo, B. U.; Kim, D. Y.; Lee, T. H.;
Eom, J. Y.; Kim, C.; Lee, K. H.; Lee, J. H. Combustion-Mediated
Synthesis of Hollow Carbon Nanospheres for High-Performance
Cathode Material in Lithium-Sulfur Battery. Carbon 2016, 103, 255−
262.
(16) He, G.; Evers, S.; Liang, X.; Cuisinier, M.; Garsuch, A.; Nazar,
L. F. Tailoring Porosity in Carbon Nanospheres for Lithium-Sulfur
Battery Cathodes. ACS Nano 2013, 7, 10920−10930.
(17) He, J.; Luo, L.; Chen, Y.; Manthiram, A. Yolk-Shelled C@
Fe3O4 Nanoboxes as Efficient Sulfur Hosts for High-Performance
Lithium-Sulfur Batteries. Adv. Mater. 2017, 29, 1702707.
(18) Dörfler, S.; Strubel, P.; Jaumann, T.; Troschke, E.; Hippauf, F.;
Kensy, C.; Schokel, A.; Althues, H.; Giebeler, L.; Oswald, S.; Kaskel,
S. On the Mechanistic Role of Nitrogen-Doped Carbon Cathodes in
Lithium-Sulfur Batteries with Low Electrolyte Weight Portion. Nano
Energy 2018, 54, 116−128.
(19) Ren, J.; Zhou, Y.; Guo, M.; Zheng, Q.; Lin, D. Novel
Sustainable Nitrogen, Iodine-Dual-Doped Hierarchical Porous
Activated Carbon as a Superior Host Material for High Performance
Lithium-Sulfur Batteries. Int. J. Hydrogen Energy 2018, 43, 20022−
20032.
(20) Xie, Y.; Meng, Z.; Cai, T.; Han, W.-Q. Effect of Boron-Doping
on the Graphene Aerogel Used as Cathode for the Lithium Sulfur
Battery. ACS Appl. Mater. Interfaces 2015, 7, 25202−25210.
(21) Shi, P.; Wang, Y.; Liang, X.; Sun, Y.; Cheng, S.; Chen, C.;
Xiang, H. Simultaneously Exfoliated Boron-Doped Graphene Sheets
To Encapsulate Sulfur for Applications in Lithium-Sulfur Batteries.
ACS Sustainable Chem. Eng. 2018, 6, 9661−9670.
(22) Li, G.; Lei, W.; Luo, D.; Deng, Y.-P.; Wang, D.; Chen, Z. 3D
Porous Carbon Sheets with Multidirectional Ion Pathways for Fast
and Durable Lithium-Sulfur Batteries. Adv. Energy Mater. 2018, 8,
1702381.
(23) Ma, F.; Liang, J.; Wang, T.; Chen, X.; Fan, Y.; Hultman, B.; Xie,
H.; Han, J.; Wu, G.; Li, Q. Efficient Entrapment and Catalytic
Conversion of Lithium Polysulfides on Hollow Metal Oxide
Submicro-Spheres as Lithium-Sulfur Battery Cathodes. Nanoscale
2018, 10, 5634−5641.
(24) Liang, X.; Kwok, C. Y.; Lodi-Marzano, F.; Pang, Q.; Cuisinier,
M.; Huang, H.; Hart, C. J.; Houtarde, D.; Kaup, K.; Sommer, H.;
Brezesinski, T.; Janek, J.; Nazar, L. F. Tuning Transition Metal Oxide-
Sulfur Interactions for Long Life Lithium Sulfur Batteries: The
″Goldilocks″ Principle. Adv. Energy Mater. 2016, 6, 1501636.
(25) Yuan, Z.; Peng, H. J.; Hou, T. Z.; Huang, J. Q.; Chen, C. M.;
Wang, D. W.; Cheng, X. B.; Wei, F.; Zhang, Q. Powering Lithium-
Sulfur Battery Performance by Propelling Polysulfide Redox at
Sulfiphilic Hosts. Nano Lett. 2016, 16, 519−527.
https://doi.org/10.1021/acsaem.0c03235
ACS Appl. Energy Mater. 2021, 4, 3487−3494
ACS Applied Energy Materials www.acsaem.org Article

(26) Lin, H.; Yang, L.; Jiang, X.; Li, G.; Zhang, T.; Yao, Q.; Zheng, Lithium Polysulfide Conversion for Lithium−Sulfur Battery. Electro-
G.; Lee, J. Y. Electrocatalysis of Polysulfide Conversion by Sulfur- chim. Acta 2020, 330, 135310.
Deficient MoS2 Nanoflakes for Lithium-Sulfur Batteries. Energy (44) Wang, S.; Liao, J.; Yang, X.; Liang, J.; Sun, Q.; Liang, J.; Zhao,
Environ. Sci. 2017, 10, 1476−1486. F.; Koo, A.; Kong, F.; Yao, Y.; Gao, X.; Wu, M.; Yang, S.-Z.; Li, R.;
(27) Chen, T.; Ma, L.; Cheng, B.; Chen, R.; Hu, Y.; Zhu, G.; Wang, Sun, X. Designing a Highly Efficient Polysulfide Conversion Catalyst
Y.; Liang, J.; Tie, Z.; Liu, J.; Jin, Z. Metallic and polar Co9S8 inlaid with Paramontroseite for High-Performance and Long-Life Lithium-
carbon hollow nanopolyhedra as efficient polysulfide mediator for Sulfur Batteries. Nano Energy 2019, 57, 230−240.
lithium-sulfur batteries. Nano Energy 2017, 38, 239−248. (45) Chen, Y.; Zhang, W.; Zhou, D.; Tian, H.; Su, D.; Wang, C.;
(28) Liu, J. D.; Zheng, X. S.; Shi, Z. F.; Zhang, S. Q. Sulfur/ Stockdale, D.; Kang, F.; Li, B.; Wang, G. Co−Fe Mixed Metal
Mesoporous Carbon Composites Combined with γ-MnS as Cathode Phosphide Nanocubes with Highly Interconnected-Pore Architecture
Materials for Lithium/Sulfur Batteries. Ionics 2014, 20, 659−664. as an Efficient Polysulfide Mediator for Lithium−Sulfur Batteries.
(29) Li, Z.; He, Q.; Xu, X.; Zhao, Y.; Liu, X.; Zhou, C.; Ai, D.; Xia, ACS Nano 2019, 13, 4731−4741.
L.; Mai, L. A 3D Nitrogen-Doped Graphene/TiN Nanowires (46) Yang, Y.; Zhong, Y.; Shi, Q.; Wang, Z.; Sun, K.; Wang, H.
Composite as a Strong Polysulfide Anchor for Lithium-Sulfur Electrocatalysis in Lithium Sulfur Batteries under Lean Electrolyte
Batteries with Enhanced Rate Performance and High Areal Capacity. Conditions. Angew. Chem., Int. Ed. 2018, 57, 15549−15552.
Adv. Mater. 2018, 30, 1804089. (47) Pei, F.; Lin, L.; Fu, A.; Mo, S.; Ou, D.; Fang, X.; Zheng, N. A
(30) Cheng, J.; Zhao, D.; Fan, L.; Wu, X.; Wang, M.; Zhang, N.; Two-Dimensional Porous Carbon-Modified Separator for High-
Sun, K. Ultra-High Rate Li-S Batteries Based on a Novel Conductive Energy-Density Li-S Batteries. Joule 2018, 2, 323−336.
Ni2P Yolk-Shell Material as the Host for the S Cathode. J. Mater. (48) Hong, X.; Mei, J.; Wen, L.; Tong, Y.; Vasileff, A. J.; Wang, L.;
Chem. A 2017, 5, 14519−14524. Liang, J.; Sun, Z.; Dou, S. X. Nonlithium Metal-Sulfur Batteries: Steps
(31) Liang, X.; Nazar, L. F. In Situ Reactive Assembly of Scalable Toward a Leap. Adv. Mater. 2019, 31, 1802822.
Core-Shell Sulfur-MnO2 Composite Cathodes. ACS Nano 2016, 10, (49) Wang, Y.-X.; Zhang, B.; Lai, W.; Xu, Y.; Chou, S.-L.; Liu, H.-K.;
4192−4198. Dou, S.-X. Room-Temperature Sodium-Sulfur Batteries: A Compre-
(32) Li, Z.; Zhang, J.; Lou, X. W. D. Hollow Carbon Nanofibers hensive Review on Research Progress and Cell Chemistry. Adv. Energy
Filled with MnO2 Nanosheets as Efficient Sulfur Hosts for Lithium- Mater. 2017, 7, 1602829.
Sulfur Batteries. Angew. Chem., Int. Ed. 2015, 54, 12886−12890. (50) Ryu, H.; Kim, T.; Kim, K.; Ahn, J. H.; Nam, T.; Wang, G.; Ahn,
(33) Rehman, S.; Tang, T.; Ali, Z.; Huang, X.; Hou, Y. Integrated H. J. Discharge Reaction Mechanism of Room-Temperature Sodium-
Design of MnO2@Carbon Hollow Nanoboxes to Synergistically Sulfur Battery with Tetra Ethylene Glycol Dimethyl Ether Liquid
Encapsulate Polysulfides for Empowering Lithium Sulfur Batteries. Electrolyte. J. Power Sources 2011, 196, 5186−5190.
Small 2017, 13, 1700087. (51) Lee, D. J.; Park, J. W.; Hasa, I.; Sun, Y. K.; Scrosati, B.;
(34) Li, Z.; Xu, R.; Deng, S.; Su, X.; Wu, W.; Liu, S.; Wu, M. MnS Hassoun, J. Alternative Materials for Sodium Ion-Sulphur Batteries. J.
Decorated N/S Codoped 3D Graphene Which Used as Cathode of Mater. Chem. A 2013, 1, 5256−5261.
the Lithium-Sulfur Battery. Appl. Surf. Sci. 2018, 433, 10−15. (52) Kim, I.; Park, J. Y.; Kim, C.; Park, J. W.; Ahn, J. P.; Ahn, J. H.;
(35) Liu, X.; Huang, J.-Q.; Zhang, Q.; Mai, L. Nanostructured Metal Kim, K. W.; Ahn, H. J. Sodium Polysulfides during Charge/Discharge
Oxides and Sulfides for Lithium−Sulfur Batteries. Adv. Mater. 2017, of the Room-Temperature Na/S Battery Using TEGDME Electrolyte.
29, 1601759. J. Electrochem. Soc. 2016, 163, A611−A616.
(36) Mohamed, S. G.; Attia, S. Y.; Barakat, Y. F.; Hassan, H. H.;
Zoubi, W. A. Hydrothermal Synthesis of α-MnS Nanoflakes@
Nitrogen and Sulfur Co-doped rGO for High-Performance Hybrid
Supercapacitor. ChemistrySelect 2018, 3, 6061−6072.
(37) Chen, X.; Zhang, J.; Zeng, J.; Shi, Y.; Lin, S.; Huang, G.; Wang,
H.; Kong, Z.; Xi, J.; Ji, Z. MnS Coupled with Ultrathin MoS2
Nanolayers as Heterojunction Photocatalyst for High Photocatalytic
and Photoelectrochemical Activities. J. Alloy. Compd. 2019, 771, 364−
372.
(38) Li, Q.; Wang, T.; Havas, D.; Zhang, H.; Xu, P.; Han, J.; Cho, J.;
Wu, G. High-Performance Direct Methanol Fuel Cells with Precious-
Metal-Free Cathode. Adv. Sci. 2016, 3, 1600140.
(39) Wang, Y.; Huang, J.; Chen, X.; Wang, L.; Ye, Z. Powder
Metallurgy Template Growth of 3D N-Doped Graphene Foam as
Binder-Free Cathode for High-Performance Lithium/Sulfur Battery.
Carbon 2018, 137, 368−378.
(40) Miao, Z.; Wang, X.; Tsai, M.-C.; Jin, Q.; Liang, J.; Ma, F.;
Wang, T.; Zheng, S.; Hwang, B.-J.; Huang, Y.; Guo, S.; Li, Q.
Atomically Dispersed Fe-Nx/C Electrocatalyst Boosts Oxygen
Catalysis via a New Metal-Organic Polymer Supramolecule Strategy.
Adv. Energy Mater. 2018, 8, 1801226.
(41) Qiu, Y.; Li, W.; Zhao, W.; Li, G.; Hou, Y.; Liu, M.; Zhou, L.;
Ye, F.; Li, H.; Wei, Z.; Yang, S.; Duan, W.; Ye, Y.; Guo, J.; Zhang, Y.
High-Rate, Ultralong Cycle-Life Lithium/Sulfur Batteries Enabled by
Nitrogen-Doped Graphene. Nano Lett. 2014, 14, 4821−4827.
(42) Ma, F.; Wan, Y.; Wang, X.; Wang, X.; Liang, J.; Miao, Z.; Wang,
T.; Ma, C.; Lu, G.; Han, J.; Huang, Y.; Li, Q. Bifunctional Atomically
Dispersed Mo−N2/C Nanosheets Boost Lithium Sulfide Deposition/
Decomposition for Stable Lithium−Sulfur Batteries. ACS Nano 2020,
14, 10115−10126.
(43) Ma, F.; Wang, X.; Wang, J.; Tian, Y.; Liang, J.; Fan, Y.; Wang,
L.; Wang, T.; Cao, R.; Jiao, S.; Han, J.; Huang, Y.; Li, Q. Phase-
Transformed Mo4P3 Nanoparticles as Efficient Catalysts towards

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