Full paper
Sodium Ion Batteries
Heteroatom-Doped Mesoporous Hollow Carbon Spheres
for Fast Sodium Storage with an Ultralong Cycle Life
Dan Ni, Wang Sun,* Zhenhua Wang, Yu Bai, Hongshuai Lei, Xinhua Lai, and Kening Sun*
Carbon materials have attracted significant attention as anode materials for
sodium ion batteries (SIBs). Developing a carbon anode with long-term cycling
stability under ultrahigh rate is essential for practical application of SIBs in
energy storage systems. Herein, sulfur and nitrogen codoped mesoporous
hollow carbon spheres are developed, exhibiting high rate performance of
144 mA h g−1 at 20 A g−1, and excellent cycling durability under ultrahigh
current density. Interestingly, during 7000 cycles at a current density of
20 A g−1, the capacity of the electrode gradually increases to 180 mA h g−1.
The mechanisms for the superior electrochemical performance and capacity
improvement of the cells are studied by electrochemical tests, ex situ transmis-
sion electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy,
and Raman analysis of fresh and cycled electrodes. The unique and robust
structure of the material can enhance transport kinetics of electrons and
sodium ions, and maintain fast sodium storage from the capacitive process
under high rate. The self-rearrangement of the carbon structure, induced by
continuous discharge and charge, lead to the capacity improvement with
cycles. These results demonstrate a new avenue to design advanced anode
materials for SIBs.
1. Introduction
The growing interest for large-scale energy-storage systems
(ESSs) has been brought by the rapidly increased demand of
renewable energy supplies, such as wind, solar, and wave.[1] The
application of lithium ion batteries in ESSs is however limited
Dr. D. Ni, Prof. W. Sun, Prof. Z. Wang, Prof. Y. Bai, Prof. K. Sun
Beijing Key Laboratory for Chemical Power Source and Green Catalysis
School of Chemistry and Chemical Engineering
Beijing Institute of Technology
Beijing 100081, China
E-mail: sunwang@bit.edu.cn; bitkeningsun@163.com
Prof. Z. Wang, Prof. K. Sun
Collaborative Innovation Center of Electric Vehicles in Beijing
Beijing Institute of Technology
Beijing 100081, China
Prof. H. Lei
Beijing Key Laboratory of Lightweight Multi-functional Composite
Materials and Structures
Beijing Institute of Technology
Beijing 100081, China
X. Lai
Yinlong Energy Co., Ltd
Zhuhai 51900, China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.201900036.
DOI: 10.1002/aenm.201900036
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by their high cost and insufficient lithium
resources.[2] As sodium is abundant and
shows similar physicochemical properties
to lithium, sodium ion batteries (SIBs)
have been recognized as a cost effective
alternative for applications in ESSs;[3]
thus, extensive research studies have been
devoted to develop high-performance elec-
trode materials for SIBs. To date, ample
potential cathode materials for SIBs have
been proposed.[4] As for anode, carbona-
ceous materials,[5] phosphorus,[6] alloy,[7]
and metal oxides[8] have been exploited
as potential SIB anode materials. Carbon
anodes are considered as the most prom-
ising choice for commercialization, owing
to their low cost and environmentally
benign nature. However, slow ion dif-
fusion kinetics and significant volume
changes, resulting from larger ionic
radius of sodium than that of lithium, lead
to poor rate and cycling performance and
hinder the practical application of most
carbon anode materials.[9] Considering
the intermittence and fluctuation nature of renewable energy
and the economic viability for ESSs, developing suitable anode
materials with fast sodium storage properties and long-term
cycle stability is a crucial issue for SIBs.[10]
To enhance the electrochemical performance of carbona-
ceous anodes, a number of strategies have been proposed.
Nanostructure construction has been considered as an effective
method, and hollow carbon spheres have been demonstrated
to be an attractive morphology for carbon materials due to
their high surface area and short sodium ion diffusion path,
which are kinetically favorable for ion and electron trans-
ports.[11] Besides, doping heteroatoms into carbon has been
recognized as a mean to modify carbon structure, as well as
to enhance electronic conductivity and wettability of carbon,
thus improving electrochemical performance.[12] Maier and
co-workers have first prepared hollow carbon spheres, which
exhibited 160 mA h g−1 under 100 mA g−1 over 100 cycles, and
50 mA h g−1 under 10 A g−1.[11a] Ye et al. have prepared hollow
carbon spheres with sulfur and nitrogen codoping, which
exhibited 169 mA h g−1 under 500 mA g−1 over 2000 cycles and
110 mA h g−1 under 10 A g−1.[11b] However, further research
on carbon-based SIB anodes with ultralong cycle life under
high current density, which are essential for the grid electricity
storage, is still needed. In addition, previous research studies
mainly focused on perfect spheres without large pores on the
surface, which would limit the electrolyte diffusion into the
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hollow sphere and prohibit the sufficient use of inner side of
the carbon wall.
Herein, sulfur and nitrogen codoped mesoporous hollow
carbon spheres (SNMHCSs) were prepared using dopamine as
a carbon source, and nano-CaCO3 as a template, which can help
generate mesopores on the carbon wall. The SNMHCSs anode
exhibits superior rate performance (144 mA h g−1 at 20 A g−1);
it also shows excellent cycling stability, delivering a reversible
capacity of 174 mA h g−1 at 0.5 A g−1 after 2000 cycles. In addi-
tion, the long-life cycle test under ultrahigh current density
of 20 A g−1 shows that the capacity gradually increases to
180 mA h g−1 after 7000 cycles. The sodium storage mecha-
nisms were quantitatively assessed, and the mechanisms of
superior rate performance, long-term cycling stability, and
improvement of capacity with increasing cycle numbers were
studied by electrochemical tests as well as ex situ transmis-
sion electron microscopy (TEM), X-ray diffraction (XRD), X-ray
photoelectron spectroscopy (XPS), and Raman analysis of fresh
and cycled electrodes.
2. Results and Discussion
2.1. Materials Synthesis and Characterization
Scheme  1 shows the typical preparation procedure of SNM-
HCSs. First, dopamine is self-polymerized, resulting in poly-
dopamine (PDA) that is uniformly coated on the surface of
CaCO3 nanoparticles, thereby forming PDA@CaCO3 precursor.
Second, the precursor is undergone hydrothermal treatment
Scheme 1.  Schematic illustration for the synthesis procedure. The inset is 2D cross-section illustration of electrons, Na+, and electrolyte transports
in SNMHCSs anode.
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with urea to add nitrogen content, and then calcined under Ar
atmosphere. During the calcination process, CaCO3 is decom-
posed to CaO, releasing CO2 gas, which causes mesopores
on the carbon wall. After removing template, nitrogen-doped
mesoporous hollow carbon spheres (NMHCSs) are obtained.
The decomposition of CaCO3 and the generation of mesopores
were confirmed by XRD patterns (Figure S1, Supporting Infor-
mation) and scanning electron microscopy (SEM) images
(Figure S2a–c, Supporting Information) of the precursors
before and after calcination or template etching process. The
PDA@CaCO3 precursor without urea treatment is calcined to
prepare mesoporous hollow carbon spheres (MHCSs) for com-
parison. SNMHCSs are obtained by treating NMHCSs under
Ar/H2S-mixed atmosphere at 650 °C. The S-doping, which can
increase the interlayer distance between carbon layers, can facil-
itate sodium ion intercalation into the carbonaceous anodes.
The inset of Scheme 1 shows that the structure of hollow
carbon sphere ensures large electrode/electrolyte contact area
for electrochemical reactions, and its mesopores can boost the
transport of electrolyte, thus can better utilize the inner side of
the hollow spheres. The well-connected carbon and thin carbon
wall can guarantee continuous electron transport and short dif-
fusion distance of Na+, respectively. These properties may play
critical roles in high rate performance.
The morphology and microstructure of SNMHCSs were
characterized by TEM and SEM analyses. The structure shows
that the interconnected hollow spheres of SNMHCSs have
diameters of 70–100 nm, and mesopores can be observed
on the carbon wall (Figure  1a; Figure S2d, Supporting Infor-
mation). The interconnected carbon can serve as a path for
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Figure 1.  a) TEM image of SNMHCSs; inset is histogram of carbon wall thickness distribution. b) HRTEM image of SNMHCSs. c) STEM image
of SNMHCSs, and d–f) are the corresponding distributions of the elemental C, N, and S. The scale bar is 100 nm.
electron transport, and the mesopores can facilitate the diffu-
sion of electrolyte. The thickness distribution shows that the
carbon wall has thickness between 5 and 15 nm with an average
value of 8.8 nm. The morphologies of SNMHCSs are similar
to NMHCSs (Figures S2c,d and S3a,b, Supporting Informa-
tion), indicating that the S-doping does not change the struc-
ture of carbon spheres. In the high-resolution transmission
electron microscopy (HRTEM) image (Figure 1b), no obvious
long-range-order structure is observed in the carbon wall of
SNMHCSs, and a number of defects are distributed within
the carbon, indicating the amorphous nature of the material.
Figure 1c–f shows the scanning transmission electron micro­
scopy (STEM) image of SNMHCSs and the corresponding ele-
ment mapping of carbon, nitrogen, and sulfur. These figures
reveal the presence and homogeneous distributions of nitrogen
and sulfur, confirming that N and S are codoped in SNMHCSs.
The morphology of MHCSs are similar to NMHCSs, indicating
that the urea treatment does not change the structure of carbon
spheres; and the carbon in MHCSs and NMHCSs is also amor-
phous (Figures S2e and S3c,d, Supporting Information).
The chemical bonds of N and S in SNMHCSs were observed
by XPS tests. The high-resolution spectrum of S2p is fitted
with three peaks (Figure 2a). The peaks at 163.8 and 165.0 eV
correspond to the S2p 3/2 and the S2p 1/2 of the CSC cova-
lent bond, and the broad peak at 168.3 eV can be assigned to
CSOxC (x  = 2–4) groups.[5c] The presence of CSC bond
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implies that the carbon matrix is doped with sulfur. The N 1s
spectrum of SNMHCSs is fitted with four peaks centered at
398.4, 400.1, 401.4, and 403.1 eV (Figure 2b), corresponding
to pyridinic-N (N-6), pyrrolic-N (N-5), graphitic-N (N-Q), and
N-oxide groups, respectively.[13] The atomic percentages of
SNMHCSs, displayed in Table S1 in the Supporting Informa-
tion, show that the N and S contents are 8.56% and 2.94%
(at%), respectively. The above results confirm that sulfur and
nitrogen were successfully introduced into carbon. Com-
pared with SNMHCSs, the N content of NMHCSs is higher
(11.02%); this indicates that the S-doping causes the N content
to decrease. The contents of N-6, N-5, N-Q in N-MHCS are
34.6%, 43.1%, and 14.1% (Figure S4a, Supporting Informa-
tion), respectively, which are different from those in SNMHCSs
(which are 44.6%, 33.7%, and 17.5%, respectively). The results
suggest that the doped S could substitute N, especially for N-5,
in the heterogeneous doped carbon.[14] The atomic percentages
of MHCSs show 5.64% N content (Table S1, Supporting Infor-
mation), suggesting that urea treatment can increase N content
by 5%. The comparison of N 1s spectrum between NMHCSs
and NMHCSs, indicates that the urea treatment mainly add
N-6 and N-5 (Figure S4, Supporting Information).
Figure 2c shows XRD patterns of SNMHCSs, NMHCSs,
and MHCSs. All XRD peaks show broad peaks of (002) diffrac-
tion, suggesting that the materials have amorphous structure.
As the (002) peak of SNMHCSs is asymmetric, it is fitted into
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Figure 2.  XPS spectra of a) S 2p and b) N 1s of SNMHCSs. XRD patterns c) and Raman spectra d) for SNMHCSs, NMHCSs, and MHCSs. e) N2
isotherms of SNMHCSs, NMHCSs, and MHCSs; inset is the corresponding DFT pore size distributions.

two peaks at 23.80° and 26.20°, and the calculated interlayer
distances (d002) are 0.373 and 0.339 nm, respectively. The XRD
peaks of NMHCSs and MHCSs are symmetry, which have
2θ values of 24.70° and 24.73°, respectively, corresponding
to interlayer distances (d002) of 0.360 and 0.359 nm, respec-
tively. The result indicates that the S-doping in the carbon
matrix can enlarge the interlayer distance of the carbon layers,
while in the same time increase the graphitization degree of
the material due to additional high temperature treatment
(650  °C for 3 h),[15] and the the increase of N content has not
changed the interlayer distance. The Raman spectroscopy was
performed to investigate the carbon structure of the materials.
As shown in Figure 2d, two strong peaks at around 1330 and
1600 cm−1 are attributed to disordered carbon (D-band) and
crystalline graphite carbon (G-band), respectively. The ID/IG
(intensity ratio of D-band and G-band), which represents the
defects in the materials, of SNMHCSs (1.19) is higher than that
of NMHCSs (1.13) and MHCSs (1.10), indicating that there
are more defects induced by S-doping in SNMHCSs, and the
N content increase by urea treatment also induce defects.[16]
As large interlayer distance is favorable for sodium storage,[17]
and high N-content can improve the reactivity and capacity of
carbon,[18] SNMHCSs is expected to display high electrochem-
ical performance when they are used as sodium ion anode.
The nitrogen isothermal adsorption–desorption meas-
urements were conducted to determine the surface area

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and pore structure of SNMHCSs, NMHCSs, and MHCSs
(Figure 2e). The isotherms of the samples are type IV, indi-
cating mesoporous structure according to the classification
by International Union of Pure and Applied Chemistry. The
Brunauer–Emmett–Teller (BET) surface areas of SNHMCSs,
NHMCSs, and HMCSs are 397, 418, and 424 m2 g−1,
respectively; the slight decrease after S-doping may be originated
from the substitution of N by a heavier atom S. The pore-size
distributions calculated using the density functional theory
(DFT) demonstrate that SNHMCSs and NHMCSs show similar
pore size distribution (inset of Figure 2e), suggesting that the
S-doping does not affect the porous structure. Mesopores with
sizes of 5 nm and about 25 nm can be observed in three sam-
ples. The 5 nm pores may be due to the interstitial space between
the particles. The mesopores around 25 nm are likely originated
from the decomposition of CaCO3 and release of CO2 during
the carbonization process. The micropores (lattice defects) cen-
tered at 1.0 nm of SNMHCSs and NMHCSs may probably be
induced by pyrolysis process,[5b] and the sodium ion adsorption
in the micropores could provide capacity at low potential pseu-
doplateau under 0.2 V.[19] It can be observed that NMHCSs have
more large micropores (>1.0 nm) than in MHCSs, which can
be attributed to the hydrothermal treatment with urea. During
the process, intermediates containing amine groups would
form,[20] which can in turn release NH3 during the carbonization
process.[21] The released NH3 would react with N-doped carbon,
leading to larger micropores in NMHCSs.[15] High surface area
and mesopores of SNHMCSs can ensure sufficient electrode/
electrolyte interface for charge-transfer reaction, convenient dif-
fusion of electrolyte, and fast sodium ion transportation.
2.2. Electrochemical Performance Characterization
The sodium storage properties and electrochemical perfor-
mances of the SNMHCSs, NMHCSs, and MHCSs samples
were investigated by cyclic voltammetry (CV) and galvanostatic
charge/discharge tests using sodium-ion half-cells. Figure S5a
in the Supporting Information shows the initial five CV curves
of SNMHCSs electrodes. The broad cathodic peak at about
1.1 V, which disappears in the followed cycles, can be attributed
to the electrolyte decomposition, the solid–electrolyte interphase
(SEI) formation, and the irreversible reactions with surface
function groups.[5c,11a,22] The peaks around 0 and 0.15 V are
resulted from the Na+ clustering into the micropores of carbon
(diffusion-controlled Na-storage).[23] In the second cycle, a broad
cathodic peak at 0.6 V, long cathodic slope, and broad anodic
peak can be observed, which could be ascribed to the insertion/
extraction of Na+ between the graphitic interlayers (diffusion-
controlled Na-storage), Na+ storage in defects or functional
groups inside the carbon (diffusion-controlled Na-storage),
and the Na+ storage on the surface of carbon (capacitive-con-
trolled Na-storage).[5c,12c,23a,24] In comparison with CV curves
of NMHCSs electrode, those of SNMHCSs electrode show two
small extra redox couples centered at around 2.17/1.56 V and
1.58/0.90 V which may be related to the redox reactions of sulfur
and sodium.[5c,23b] The CV curves of NMHCSs and MHCSs
electrode are similar, suggesting the same reaction mechanism
of the two electrodes (Figure S5b,c, Supporting Information).
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The first five galvanostatic charge and discharge curves of
the three electrodes at 0.5 A g−1 are displayed in Figure S5d–f
in the Supporting Information. The discharge profiles show
slope curves, implying that the capacity is mainly from the
intercalation of Na+ into the enlarged graphitic layers of carbon
and Na+ storage on the carbon surface due to high surface
area.[11c,12c] The reversible insertion of Na+ into the graphitic
carbon layers of SNMHCSs electrode was confirmed by ex situ
Raman spectroscopic analysis (Figure S6, Supporting Infor-
mation). The red-shift of G-band observed after sodiation indi-
cating that the elongation of CC bond, which is due to Na+
insertion into negatively charged graphitic carbon layers.[19]
After desodiation, the position of G-band returns to the posi-
tion of pristine material, indicating that the intercalation
reaction is reversible. The ID/IG ratio decreases to 1.10 after
sodiation, while increases to 1.13 after desodiation, suggesting
that the graphitic carbon layers are better aligned as a result
of intercalation-induced rearrangement/ordering.[25] The first
discharge /charge capacity of SNMHCSs is 965/280 mA h g−1
and initial coulombic efficiency (CE) electrode is 29%, which
is higher than those of NMHCSs electrode (930/185 mA h g−1
and 19.8%) and MHCSs electrode (680/160 mA h g−1 and
23%). The large irreversible capacity can be ascribed to the
irreversible reactions with surface functional groups, the SEI
layer formation, and the irreversible intercalation of Na+.[11a,25]
The results indicate that the S-doping can increase capacity
and reduce the irreversible reaction in the first cycle; and the
higher N content is favorable to achieve higher capacity, while
more irreversible reaction is brought by induce of N. However,
more studies are required to further improve the low initial
CE of SNMHCSs.
Figure  3a presents the sodium storage performance of
the three electrodes at different current densities from 0.5 to
30 A g−1. The SNMHCSs electrode exhibits reversible capaci-
ties of 240, 208, 180, 157, 147, 144, and 138 mA h g−1 at the
current densities of 0.5, 1, 2.5, 5, 10, 20, and 30 A g−1, respec-
tively. When the current density is reduced to its original value
of 0.5 A g−1, the reversible capacity of 216 mA h g−1 is obtained.
The NMHCSs electrode exhibits lower capacities of 169,
146, 127, 117, 113, 123, and 132 mA h g−1, respectively,
and MHCSs electrode exhibits 140, 115, 98, 90, 80, 83, and
91 mA h g−1, respectively. The charge–discharge curves of SNM-
HCSs, NMHCSs, and MHCSs show similar sloping curves at
different current density (Figure S7, Supporting Information).
The results further confirm that the S-doping and N-doping can
improve the capacity.
The long-term cycling tests were subsequently carried out
to evaluate the cycling stability of the samples (Figure 3a).
After 2000 cycles under a current density of 0.5 A g−1,
the SNMHCSs electrode exhibits a reversible capacity of
176 mA h g−1, the NMHCSs electrode exhibits a capacity of
144 mA h g−1, and the MHCSs electrode exhibits a capacity
of 103 mA h g−1 after 1500 cycles. The long-life cycling test
under ultrahigh current density of 20 A g−1 was conducted
on SNMHCSs electrode (Figure 3b). After several activation
cycles under 0.5 A g−1, the capacity remains at 150 mA h g−1;
and after 7000 cycles, the capacity gradually increases to
180 mA h g−1. The increased capacity of the SNMHCSs
may possibly due to the interlayer distance expansion of
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Figure 3. a) Rate cycling performances of SNMHCSs, NMHCSs, and MHCSs electrodes. b) Cycling performance and the corresponding coulombic
efficiency of SNMHCSs electrode at 20 A g−1. The electrodes were charged/discharged between 0.01 and 3.0 V (vs Na+/Na). CV curves of c) fresh
SNMHCSs electrode and d) cycled SNMHCSs electrode (7000 cycles under 20 A g−1) at different scan rates from 0.1 to 2.0 mV s−1. e) Relationship between
the peak current and the scan rate. f) Capacitive and diffusion-controlled capacity contributions for SNMHCSs electrode at 0.5 V at different scan rates.

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the polydopamine-derived carbon during cycling.[26] The
above results are among the best of carbon anodes ever
reported for high-rate and long-term cycle SIBs application
(Table S2, Supporting Information), indicating that SNM-
HCSs are promising candidates for anode of SIBs.
To obtain more comprehensive data on the superior rate
capability, long-term cycling stability and capacity increases
with cycling of SNMHCSs electrodes, the sodium storage
mechanisms of fresh and cycled electrodes (after 7000 cycles
at 20 A g−1) were studied by CV based on the works reported
by Dunn and co-workers (Figure 3c,d).[27] The capacities of the
carbon anode consist of the diffusion-controlled capacity and
the surface-induced capacitive-controlled capacity.[23] The rela-
tionship between the current (i) and the scan rate (v) follows
the power-law, which can be expressed as i = a vb; where a and b
are the adjustable parameters. When b-value approaches 1.0,
the capacitive process is dominant, and when b-value is close
to 0.5, the electrochemical process is mainly controlled by
diffusion.[23b,28] The cathodic peak current and the scan rate
(in logarithmic form) has linear relationship (Figure 3e). The
b-value of fresh SNMHCSs electrode is 0.74, while that of
cycled electrode is 0.72, suggesting that the capacity of SNM-
HCSs electrodes comes from both the diffusion-controlled
reaction and surface-induced capacitive behavior. Moreover, the
contribution of diffusion-controlled capacity in cycled electrode
is higher than that in fresh electrode.
The contribution ratios of capacitive capacity and the diffu-
sion-controlled capacity was further quantitatively determined
by separating the current (i) under a given potential (V) into
intercalated charge (k2v1/2) and capacitive charge (k1v), based
on the equation: i (V )  = k1v + k2v1/2.[8a] The exact contribu-
tion ratios of fresh and cycled electrodes at 0.5 V at different
scan rates were determined, and the results are shown in
Figure 3f. Under higher scan rate, the capacitive contribu-
tions of the fresh and cycled electrodes are higher, indicating
that structure of SNMHCSs is beneficial for the surface-
induced capacitive process under high current density. As
the capacitive process is essential in fast sodium storage and
stable cycling, the superior rate and long-life cycling capa-
bility can be attributed to the unique and stable structure
of SNMHCSs.[13a,29] Additionally, the diffusion-controlled
capacity is higher in cycled electrodes (48.2%, 29.5%, and
17.2% at scan rates of 0.1, 0.5, and 2.0 mV s−1, respectively)
than that in fresh electrode (45.3%, 27.1%, and 15.7%, respec-
tively), hinting that the sodium diffusion inside the carbon is
enhanced considering the total capacity increase.
To explore the mechanisms of long-term cycle stability, as
well as the capacity increase with cycling, the ex situ TEM
and XRD tests were carried out to examine the morphology
and structure change of SNMHCSs electrodes after cycling.
The TEM images of cycled SNMHCSs electrodes (com-
pletely desodiated) are shown in Figure  4a–c. The images
reveal that the SNMHCSs can maintain their intercon-
nected hollow sphere structures as well as their mesopores
after cycling; this proves that they have excellent structural
stability, despite long-term cycling. The average thickness
of carbon wall increases from 8.8 nm (in pristine materials)
to 15.5 nm after 7000 cycles (insets of Figure 4a–c). The
HRTEM image of cycled SNMHCSs (Figure S8, Supporting
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Information), which shows that they have amorphous
structure of pristine material, confirms that the carbon
have high structural stability. The ex situ XRD are used to
evaluate the changes of interlayer distance after cycling. The
(002) peak of cycled electrode, which is also broad, confirms
its amorphous nature; and it can be fitted into two peaks of
21.80° and 26.20°. The calculated interlayer distance (d002)
corresponding to the first peak is 0.408 nm, which is larger
than that of 0.373 nm of the pristine electrode, indicating the
expansion of the interlayer distance after cycling (Figure 4d).
This expansion of the interlayer distance could explain the
increase of carbon wall thickness of cycled electrodes.[26] The
expanded spacing between carbon layers may accommodate
more Na+ and facilitate the ion transport, thus leading to
capacity increase. In addition, the expansion volume can be
buffered by the hollow sphere structure, which is crucial for
long-term cycling stability.
To study the influence of high rate discharging/charging
on carbon structure, cycled SNMHCSs electrodes (com-
pletely desodiated) were subjected to ex situ XPS analysis
and Raman spectroscopic. The ex situ C 1s XPS spectra of
SNMHCSs electrodes, which were taken after Ar+ ions sput-
tering to avoid the influence of SEI layer, are displayed in
Figure 4e. The peaks donating sp2 C (284.8 eV), sp3 C/CH2
(285.5 eV), CO/CN (285.9 ± 0.1 eV), CO (287.0 ± 0.1 eV),
COOR (288.5 ± 0.1 eV), and CF (290.5 ± 0.1 eV from PVDF
binder) functional groups were deconvoluted.[19,30] However,
recent research shows that the SEI film in defective carbon
can't be completely sputtered away.[31] Since the sp2 C con-
tent in SEI film is significantly lower than that in carbon
material,[19,30f,31] the residual SEI film would decrease sp2 C
content in the electrode. The increase of sp2 C content (from
53.9% in pristine electrode to 62.0% of cycled electrode),
could result from the increase of sp2 C content from carbon
material, which indicates the better aligned graphitic layers
in cycled electrode.[30e] The Raman spectra show that there
are no obvious shifts in the D-band or G-band after cycling,
indicating that the carbon can maintain its structural stability
during the ultralong cycling period (Figure 4f). The ID/IG
ratio decreases with cycling, revealing that the graphitic
carbon layers have better alignment, which is consistent with
the XPS results.[13a,32]
Electrical impedance spectroscopic (EIS) of the SNMHCSs
electrodes before and after 20 A g−1 cycling were measured
to gain more insights into the electrochemical performance
(Figure 4g). The semicircle at medium-high frequency range
has been differentiated to charge-transfer resistance (Rct) and
SEI resistance (Rf) using equivalent circuit model in Figure S9a
in the Supporting Information,[33] and the results are sum-
marized in Table S3 in the Supporting Information. The Rct
decreases from 415 Ω of fresh cell to 11.7 Ω of cycled cell, sug-
gesting a faster charge-transfer after cycling, which can lead to
the decrease of polarization. The diffusion coefficient of Na+
ions (DNa) of the electrode is evaluated and compared using
EIS data, and the relevant details are given in Figure S9 in the
Supporting Information and the explanatory text in the Sup-
porting Information.[34] The DNa of SNMHCSs electrode after
7000 cycles is about 200 times higher than that of fresh cells,
and about 24 times higher that of electrode after 1000 cycles.
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advenergymat.de

Figure 4.  Ex situ TEM images of SNMHCSs electrode after a) 1000 cycles, b) 4000 cycles, and c) 7000 cycles; insets are the distribution histograms
of carbon wall thickness. d) Ex situ XRD pattern and e) ex situ XPS spectrum of C 1s of SNMHCSs after 7000 cycles in comparison with that of
pristine electrode. f) Ex situ Raman spectra and g) Nyquist plots of SNMHCSs electrode after 1000, 4000, and 7000 cycles in comparison with
those of pristine electrode. The electrodes were charged/discharged between 0.01 and 3.0 V (vs Na+/Na) at 20 A g−1. h) Schematic illustration of
the structure change of SNMHCSs electrode and the transports of Na+ and electrons in SNMHCSs before and after cycling.

The results confirm that the sodium diffusion kinetics are
faster after cycling.
Based on the above results, the mechanism for the superior
rate and long-term cycling performance as well as the increase
of capacity with cycling can be summarized, and a schematic
illustration for the mechanism is presented in Figure 4h for
better comprehension. The interconnected hollow sphere struc-
ture with mesopores can facilitate the transport of electrons,
sodium ions as well as electrolyte, the enlarged interlayer dis-
tance by S-doping can improve the intercalation kinetics of
sodium ion, and the N-doping can increase capacity. The robust
structure can buffer the volumetric change of SNMHCSs
electrode after cycling, thus can stabilize its structure. As a
result, the electrode can maintain its large surface area and
ensure the fast sodium storage from surface-induced capaci-
tive process. Thus, the excellent electrochemical performances
were achieved. After cycling, the expanded interlayer dis-
tance can facilitate the transport of sodium ion, and the better
aligned graphitic layers can enhance electronic transfer as well
as provide better alignment ionic transport path between the
carbon layers, leading to faster charge transfer.[30e] These results
correspond with the decrease of Rct, increase of DNa and the
increased diffusion-controlled capacity after cycling, thereby
can explain the increase of capacity.

Adv. Energy Mater. 2019, 1900036 1900036  (8 of 10) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
3. Conclusion
Sulfur- and nitrogen-codoped mesoporous hollow carbon
spheres (SNMHCSs) were successfully prepared by using
low-cost CaCO3 nanoparticles as self-sacrifice templates and
polydopamine as carbon precursor; and the mesopores on
the carbon wall were generated during calcination process.
When used as SIBs anode materials, the SNMHCSs exhibit
remarkable rate performance (240, 208, 180, 157, 147, 144,
and 138 mA h g−1 at current densities of 0.5, 1, 2.5, 5, 10, 20,
and 30 A g−1, respectively), and outstanding cycling stability
(174 mA h g−1 after 2000 cycles under a current density 0.5 A g−1,
and 180 mA h g−1 after 7000 cycles under a current density
20 A g−1). The unique interconnected mesoporous hollow
sphere structure can provide large electrode/electrolyte inter-
face for reaction, facilitate the diffusion of electrolyte, increase
the transport rate of electrons and sodium ions, and buffer the
volumetric expansion of electrode during cycling; as a result,
the excellent rate and cycling performance is achieved. Sulfur
doping, which increases the interlayer distance between the
carbon layers, can enable carbon to accommodate more sodium
ions and promote ion transports; while nitrogen doping, which
can add the functional groups and defects, can increase the
capacity. Additionally, during continuous charge and discharge
process, the increased interlayer distance between carbon layers
and the better alignment of graphitic carbon layers occurred,
resulting in fast charge transfer and increased capacity of elec-
trode with increasing numbers of cycles. The excellent electro-
chemical performance ensures SNMHCSs promising anode
materials for high performance SIBs. The design strategy and
the improvement mechanism reported in this work, could
be extended to other energy storage systems where structure
robustness and fast electron/ion transport are urgently needed.
4. Experimental Section
Preparation of Materials: First, 120 mg of 2-amino-2-hydroxymethyl-
propane-1,3-diol (Tris; Aladdin) and 500 mg of commercial hydrophilic
CaCO3 nanoparticles (Shanxi Xintai NanoMater. Co., Ltd.) were
dispersed in deionized water (100 mL) and then stirred for 5 h at room
temperature. Then, 400 mg of dopamine hydrochloride (Aladdin) was
added into the solution and stirred for 36 h at room temperature. The
resulting product was centrifuged and washed with deionized water and
ethanol, and thereafter was subjected to vacuum drying at 60 °C for 12 h.
The dry PDA@CaCO3 precursor and 1.8 g of urea were dispersed
in deionized water (30 mL), and the pH value of the solution was
adjusted to 10 using NH3·H2O. After continuous stirring for 60 min,
the solution was transferred to a Teflon-lined stainless steel autoclave
(50 mL) for hydrothermal treatment at 120 °C for 12 h. The products
were centrifuged, washed, and vacuum dried at 60 °C for 12 h. The
dried products were heated at 450 °C for 3 h (1 °C min−1), and then
annealed at 800 °C for 3 h (5 °C min−1) under Ar atmosphere. Finally, the
powders were etched with 1 m HCl solution for 1 h. The products were
collected by centrifugation, and then vacuum dried at 60 °C for 12 h to
obtain NMHCSs. The SNMHCSs were synthesized by treating NMHCSs
under H2S/Ar (5/95%) gas at 650 °C for 3 h (5°C min−1). MHCSs were
prepared through calcinating PDA@CaCO3 precursor without urea
treatment, followed by the same etching and vacuum drying process.
Characterization of the Materials: SEM (Hitachi, SU8010) and TEM
(JEOL, JEM-2100F, 200 kV) were employed to observe morphologies
of the prepared materials. XPS measurements (Physical Electronics
Adv. Energy Mater. 2019, 1900036 1900036  (9 of 10)
www.advenergymat.de
5400 ESCA) were carried out to determine the chemical composition
of the products. The XPS spectra of the pristine and cycled electrodes
were taken after 2000 eV Ar+ ion sputtering in ultrahigh vacuum to avoid
the influence of SEI layer and surface oxidation during the manufacture
process, using a ESCALAB 250Xi. The structural information of the
materials was obtained by XRD (Rigaku Ultima IV) with a Cu Kα radiation
source (V  = 40 kV, I  = 40 mA) and HRTEM. Raman spectroscopy was
performed on a Renishaw with a 633 nm laser. The BET surface area
and pore size distribution were measured using an ASIQM0VH002-5
analyzer (Quantachrome).
Electrochemical Measurements: The measurement of electrochemical
performance of the materials was carried out using coin cells (CR2025-
type). The electrodes were prepared by mixing active materials, carbon
black, and polyvinylidene fluoride at a weight ratio of 80:10:10 in N-methyl-
2-pyrrolidone (NMP), which was used as a solvent to obtain a slurry. The
slurry was then coated onto clean copper foil and dried at 100 °C for
24 h under vacuum. The typical mass loading was ≈0.3–0.4 mg cm−2.
The coin cells were assembled using metallic sodium as a counter
electrode, GF/D-type glass fiber (Whatman) as a separator, and NaClO4
(1 m) in ethylene carbonate (EC)/diethyl carbonate (DEC) (EC:DEC =
1:1, v/v) with 2% fluoroethylene carbonate (FEC) as electrolyte.
Galvanostatic discharge and charge tests were carried out at various
current rates at the potential range of 1.5–4.5 V (vs Na+/Na) using a
Land CT2001A testing system. CV measurements were performed on an
electrochemical workstation (CHI 660E, Shanghai Chenhua Instrument)
at the voltage range of 0.01–3.0 V. The EIS tests were conducted using
a Parstat 2273 electrochemical system, operated at a frequency range of
100 kHz to 10 mHz and at a 10 mV AC signal amplitude.
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (Grant Nos. 21576028, 21506012, and 51802018)
and the Program for Innovative and Entrepreneurial team in Zhuhai
(Grant No. ZH01110405160007PWC). The authors also thank Analysis
&Testing Center, Beijing Institute of Technology.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
anodes, heteroatom doping, hollow carbon spheres, mesopores, sodium
ion batteries
Received: January 4, 2019
Revised: February 26, 2019
Published online:
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