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Core–Shell FeSe2/C Nanostructures Embedded in a
Carbon Framework as a Free Standing Anode for a Sodium
Ion Battery
Muhammad Yousaf, Zhipeng Wang, Yunsong Wang, Yijun Chen, Usman Ali,
Muhammad Maqbool, Ali Imran, Nasir Mahmood, Peng Gao,* and Ray P. S. Han*
Embedding the functional nanostructures into a lightweight nanocarbon
framework is very promising for developing high performance advanced
electrodes for rechargeable batteries. Here, to realize workable capacity, core–
shell (FeSe2/C) nanostructures are embedded into carbon nanotube (CNT)
framework via a facile wet-chemistry approach accompanied by thermally
induced selenization. The CNT framework offers 3D continuous routes for
electronic/ionic transfer, while macropores provide adequate space for high
mass loading of FeSe2/C. However, the carbon shell not only creates a solid
electronic link among CNTs and FeSe2 but also improves the diffusivity of
sodium ions into FeSe2, as well as acts as a buffer cushion to accommodate
the volume variations. These unique structural features of CNT/FeSe2/C
make it an excellent host for sodium storage with a capacity retention of
546 mAh g−1 even after 100 cycles at 100 mA g−1. Moreover, areal and volu-
metric capacities of 5.06 mAh cm−2 and 158 mAh cm−3 are also achieved at
high mass loading 16.9 mg cm−2, respectively. The high performance of multi-
benefited engineered structure makes it a potential candidate for secondary
ion batteries, while its easy synthesis makes it extendable to further complex
structures with other morphologies (such as nanorods, nanowires, etc.) to
meet the high energy demands.
1. Introduction
Sodium ion battery (SIB) is considered a good alternative to the
lithium ion battery (LIB) in terms of its similar charge storage
mechanism but at a lower cost (estimated cost reduction of
Dr. M. Yousaf, Prof. P. Gao
International Center for Quantum Materials and Electron
Microscopy Laboratory
School of Physics
Peking University
Beijing 100871, China
E-mail: p-gao@pku.edu.cn
Dr. M. Yousaf, Z. Wang, Dr. Y. Wang, Dr. Y. Chen, U. Ali, M. Maqbool,
Prof. R. P. S. Han
Department of Material Science and Engineering
Peking University
Beijing 100871, China
E-mail: ray-han@pku.edu.cn
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/smll.202002200.
DOI: 10.1002/smll.202002200
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4.3%)[1] due to the natural abundance of
Na (20 ppm for Li and 23 600 ppm for
Na).[2–3] However, many factors such as
the small charge storage capacity, low
mass loading, and sluggish kinetics of Na
ion in current electrode materials limit its
practical applications.[4–6] Various anode
chemistries have been explored, which are
classified into three main groups based
on their charge storage mechanism, that
is, intercalation-type (e.g., graphite, lay-
ered materials), alloy-type (e.g., Sn, Si,
Ge), and conversion-type (e.g., Fe2O3,
FeS2, MoS2).[7–8] Unfortunately, limited
space in intercalation materials and huge
volume changes in alloying hosts put
them behind the most favorable conver-
sion chemistry due to their large capacity
and low mechanical strains. Therefore,
facile approaches need to be developed for
designing new electrode materials based
on conversion-type chemistries which are
appropriate to realize the storage ability of
SIBs comparable to that of LIBs.
Recently, transition metal selenides
(TMSe) are found highly suitable for sodium storage due to
their large theoretical capacities (>450 mAh g−1) and compa-
rably high conductivities.[9–10] Moreover, TMSe did not suffer
from the poly-sulfide anion shuttle effect that is normally asso-
ciated with sulfide type anodes.[11] Taking an example of TMSe,
Dr. A. Imran
Artificial Micro and Mesoscopic Physics
School of Physics
Peking University
Beijing 100871, China
Dr. N. Mahmood
School of Engineering
RMIT University
124 La Trobe Street, Melbourne, Victoria 3001, Australia
Prof. R. P. S. Han
Cancer Research Center
Jiangxi University of Traditional Chinese Medicine
Nanchang 330004, China
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FeSe2 is highly attractive as an anode for SIBs due to a large
abundance of Fe, low toxicity, environment benignity, good
chemical stability, selenium-rich structure and high theoretical
capacity (501.5 mAh g−1).[12] However, FeSe2 also possesses low
intrinsic conductivity and suffers from large volume variations.
These issues become crucial as high mass loading is required
for commercial applications; therefore, to have control over
structural pulverization and formation of unstable and inhomo-
geneous solid electrolyte interface (SEI) film, better designing
of electrode materials are needed.
Until now, a lot of efforts have been devoted to overcoming
these issues by developing various compositions of FeSe2−x in
different morphologies, moreover, blended with various mate-
rials.[13–16] However, higher surface area increases the chances
for agglomeration of these nanostructured materials as well
as causes intensive side reactions during the sodiation/de-
sodiation process.[17] An inner conductive coating over the sur-
face is a well-accepted approach to alleviate this issue, which
is favorable in preventing side reactions, reducing inter-particle
resistance and agglomeration.[18–19] However, blending of
this conductive powder with binder to construct an electrode
reduces the overall conductivity of electrode, thus abolishing
the benefit of additional coating. Moreover, such designing of
electrode materials limits the mass loadings to very low value
(≤1.5 mg cm−2), resulting in low areal and volumetric capaci-
ties.[20] To circumvent these issues, impeding of various nano-
structures (nanowires, nanosheets, or nanoparticles) inside the
3D carbon matrix is an effective approach.[21–23] However, the
direct incorporation of active materials into the carbon matrix
may cause a detachment during the electrochemical process
and result in agglomeration, hence capacity fading. Thus, a
strong pining point needs to develop like individual carbon
cage for each nanostructure inside the 3D carbon matrix,
may resolve all issues, and result in free-standing ready to use
electrodes.
Figure 1. Fabrication process of CNT/FeSe2/C.
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Although, layered transition metal chalcogenides (TMCs)
have been deposited on carbon nanotube (CNT)[24] and carbon
nanofiber (CNF),[25] but uniform deposition of highly crystalline
nanoparticles (NPs) of non-layered TMCs on 3D porous CNT
without any aggregation is a big challenge due to several factors:
(i) poor penetration of various precursors (Fe and Se precur-
sors) solutions into the 3D CNT framework (ii) weak physical
bonding of active material with CNT, and (iii) active mate-
rial must possess adequate surface and adsorption energies to
attach on the solid substrate. Besides, previously carbon coating
on simple systems or layered materials was carried out which
is easy,[24–25] but to realize it on complex foam especially coated
with particles as NPs coating provides variable nucleation site
therefore homogenous coating of amorphous carbon is difficult.
Herein, an easy and stepwise methodology is developed to
realize a cage-inside-a-cage to overcome most of the challenges
associated with SIBs, while active material is decorated in the
core cage through a simple method. A double cage protec-
tion and a free-standing electrode is fabricated in three steps:
(i) hydrothermal grafting of Fe2O3 onto the CNT framework,
(ii) thermal-induced selenized conversion of Fe2O3 into FeSe2,
and (iii) coating of an amorphous carbon layer over FeSe2
NPs and spreading onto individual CNTs by carbonization
(Figure 1). (iv) the thickness of amorphous shell was kept as
low as possible so it allows faster ionic flow and provides suf-
ficient electronic conductivity. Moreover, the incorporation of
FeSe2/C into the CNT does not affect the structural integrity of
the hybrid thus, retaining the ability to greatly improve the Na+
ion storage. High porosity between the individual CNTs offers
large mass loadings while the intimate contact between the
carbon core and FeSe2 shell controls the SEI film and buffers
the volume expansion/contraction. The highly compressible
and 3D porous CNT/FeSe2/C hybrid could be densified to
obtain ultra-high areal mass loadings up to 16.9 mg cm−2 cor-
responding to areal capacity of 5.06 mAh cm−2. It therefore
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highlights the benefits of easy structural manipulation to investigate the influence of amorphous carbon coating on
develop high performing electrode materials for future energy anode performance by controlling the concentration of glucose
storage systems. in the precursor solution. A schematic sketch of the fabrication
of CNT/FeSe2/C is shown in Figure 1.

2. Results and Discussion H2 + Se → H2Se (1)

To obtain 3D porous CNT/FeSe2/C hybrid, initially, Fe2O3
NPs are impulsively grown and grafted on the individual CNT
(CNT/Fe2O3) via a hydrothermal process, where CNTs are pre-
sent in the form of a 3D framework. Afterward, a thermal-
induced selenization was carried out to convert solid Fe2O3
NPs to porous FeSe2 NPs at the surface of CNTs, so that the
larger ions can easily move in and out of NPs. At high tempera-
ture, that is, 500 °C, Se powder reacted with incoming H2 gas
to produce H2Se gas (Equation (1)), which is a strong reducing
agent and spontaneously transformed the Fe2O3 NPs into FeSe2
NPs via Kirkendall diffusion effect (Equation (2)).[26] In the
end, an amorphous carbon layer is encapsulated on the CNT/
FeSe2 simply by the glucose carbonization process. Further,
three composites with different amorphous carbon contents
of 0 wt% (CNT/FeSe2), 8.0 wt% (CNT/FeSe2/C-1) and 17.6 wt%
(CNT/FeSe2/C-2) were fabricated at optimized conditions to
11H2Se + 2Fe 2 O3 → 4FeSe 2 ( s ) + 11H2 ( g ) + 3SeO2 ( g ) (2)
The scanning electron microscope (SEM) image of pris-
tine CNT framework reveals its 3D interconnected porous
network which is highly suitable as host for the growth of
NPs (Figure S1, Supporting Information). The SEM image of
CNTs/Fe2O3, confirm the fine growth of Fe2O3 NPs on the sur-
face of CNTs with an average size of ≈50 nm (Figure 2a). It is
also observed that Fe2O3 NPs are homogeneously distributed
throughout the 3D CNTs network. The flexible and mechani-
cally robust nature of CNTs helped in the thermal conversion
of Fe2O3 to FeSe2 without adversely impacting on the frame-
work structure (Figure 2b). Figure 2c reveals that carbon is uni-
formly coated on each FeSe2 NPs as well as individual CNT to
result in highly conductive and dually protected structure. The
transmission electron microscope (TEM) results show that a

Figure 2. Surface and structural characterizations: SEM images of a) CNT/Fe2O3, b) CNT/FeSe2, and c) CNT/FeSe2/C frameworks, respectively.
d,e) TEM images of CNT/FeSe2,. f,g) low magnification TEM and h) HRTEM images of CNT/FeSe2/C, respectively. i) XRD pattern of CNT/FeSe2 and
CNT/FeSe2/C.

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porous structure is obtained with a little effect on the particle
size after converting Fe2O3 (≈50 nm) into FeSe2 (≈80 nm) due
to the ripening of NPs under thermal selenization process
(Figure 2d,e). A TEM image of CNT/FeSe2/C indicates that
FeSe2 NPs are strongly attached to the CNT as evident from
Figure 2f, having an ≈2.8 nm thick amorphous carbon coat
(Figure 2g,h). A d-spacing of 3.37 Å was observed in the high
resolution TEM (HRTEM) image of CNT/FeSe2/C that corre-
sponds to the (120) lattice plane of FeSe2 (Figure 2g). The crystal
structure of the hybrid frameworks at each stage during the
preparation of CNT/FeSe2/C was analyzed by X-ray diffraction
(XRD). Figure S2, Supporting Information shows the XRD pat-
terns of the CNT/Fe2O3 and is indexed well to the maghemite-C
phase of Fe2O3 (JCPDS # 39–1346), revealing crystalline growth
of Fe2O3 NPs. The XRD patterns of CNT/FeSe2 and CNT/
FeSe2/C are shown in Figure 2i. All characteristic peaks in both
hybrids are well consistent with the orthorhombic phase of
FeSe2 (JCPDS # 82–0269) with preferential growth along (120)
plane. In addition to the characteristic peaks of orthorhombic
FeSe2, only one peak at 27.3° that corresponds to the (002) plane
of the CNT is seen, delineating high crystallinity of FeSe2 and
purity of the composites. Nevertheless, a decrease intensity of
peaks in CNT/FeSe2/C compared with CNT/FeSe2 additionally
guarantees the coating of carbon shell on FeSe2 (Figure 2i).
Three characteristics peaks located at 180.1, 214.8, and
254.1 cm−1 were observed for FeSe2 in the Raman spectra of
CNT/FeSe2/C (Figure 3a). These three peaks are attributed to
the vibrational and stretching vibrations of SeSe active modes
or their combinations.[27–28] The Id/Ig ratio of CNT/FeSe2/C
Figure 3. Chemical analysis of hybrid frameworks: a) Raman spectra of CNT/FeSe2/C and CNT. XPS of CNT/FeSe2/C: high resolution spectra of b) Fe
2p, c) Se 3d, and d) C 1s, respectively. e) TGA measurements of various materials. f) BET surface area of CNT/FeSe2 and CNT/FeSe2/C.
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(0.79) is higher compared with pure CNT framework that could
be ascribed to attachment of NPs and presence of defects in
outer carbon shell coating, which contribute to the capacity. The
X-ray photoelectron microscope (XPS) survey spectrum of the
CNT/FeSe2/C is presented in Figure S3, Supporting Informa-
tion, which confirms the presence of Fe, Se, C, and O elements
in the hybrid framework without any detectable impurity. High
resolution XPS spectra of Fe 2p, Se 3d, and C 1s are shown in
Figure 3b–d. The deconvolution of Fe revealed two main peaks
located at binding energies of 706.97 and 719.84 eV, respectively,
which can be assigned to Fe 2p3/2 and Fe 2p1/2 with a spin-orbit
energy separation of about 12.87 eV (Figure 3b), demonstrating
the characteristic of divalent iron (Fe2+).[26,29–30] The minor and
broad peak at about 710.6 eV can be ascribed to the FeO bond
that exhibits the existence of a higher oxidation state of the Fe
species in the hybrid framework.[31–32] Similarly, the minor peak
in Se 3d spectrum at 58.99 eV was detected (Figure 3c), which
also reveals that the selenium surface was partially oxidized
when exposed to air.[31–32] Moreover, the binding energies at
54.48 and 55.32 eV correspond to Se 3d5/2 and Se 3d3/2, respec-
tively in Se 3d spectrum, suggesting the presence of Se2−. The
C 1s spectrum was fitted with 3 peaks: sp2 or CC, sp3 or CC,
and CO corresponding to the binding energy of 284.4, 285.1,
and 286.9 eV, respectively (Figure 3d).[33–34]
The calculation of the active weight in the hybrid is impor-
tant, and it is determined by thermogravimetric analysis (TGA)
measurement in the air. In the case of the CNT/Fe2O3 frame-
work, the measured amount of Fe2O3 is about 62% (Figure 3e).
Whereas, in CNT/FeSe2, CNT/FeSe2/C-1, CNT/FeSe2/C-2, the
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weight changes in various steps (Figure 3e). In the first step,
the weight slightly increased between 230 and 280 °C, corre-
sponding to the partial oxidation of FeSe2 and the formation of
FeSeOx.[35] However, with increase in temperature form 280 to
620 °C, a major weight loss occurred attributed to the conver-
sion of both FeSe2 and FeSeOx to Fe2O3 and combustion of CNT
and amorphous carbon in the air. Based on final product Fe2O3,
the content of carbon (due to CNT) in CNT/FeSe2 is 13.5%, and
in CNT/FeSe2/C-1 and CNT/FeSe2/C-2, they increased to 21.5%
and 31.1%, respectively. The amount of amorphous carbon
coating in CNT/FeSe2/C-1 and CNT/FeSe2/C-2 composites is
8.0% and 17.6%, respectively. Further, to investigate the advan-
tage of the carbon layer over FeSe2, the Brunauer-Emmett-Teller
(BET) surface area and pore size distribution by the Barrett-
Joyner-Halenda (BJH) method of both hybrids was estimated.
The calculated specific surface area for CNT/FeSe2 composite is
15.15 m2 g−1, while for CNT/FeSe2/C it is 67.67 m2 g−1 (Figure 3f).
The increased surface area in the case of CNT/FeSe2/C is attrib-
uted to coating of amorphous carbon layer, which makes them
suitable for mass transport. The average pore diameter of CNT/
FeSe2/C (3.827 nm) is slightly larger than the diameter of CNT/
FeSe2 (3.412 nm) and the pore volume of CNT/FeSe2/C is also
increased to 0.136 cc g−1 from the initial 0.058 cc g−1 (Figure S4,
Supporting Information). It further confirms the uniform and
firm coating of the outer carbon layer on individual FeSe2 NPs,
which can optimize the contact with the electrolyte and improve
the electrochemical performance.
To study the electrochemical Na storage behavior of the
hybrid frameworks, coin-type cells (CR2032) were manufac-
tured. Figure 4a shows the cyclic voltammetry (CV) curves
of the CNT/FeSe2/C framework for the initial four cycles at a
scan rate of 0.2 mV s−1 in the potential range of 0.01–3.0 V. In

Figure 4. Electrochemical measurements of various electrodes: a) CV curves for the first 4 cycles at a scan rate of 0.2 mV s−1. b) Potential profiles at
100 mA g−1 of CNT/FeSe2/C c) Comparison of cycling performance of different electrodes. d) Coulombic efficiency and cyclic performance of CNT/
FeSe2/C at high current density, 500 mA g−1. e) The rate capability of CNT/FeSe2/C. f) Schematic illustration of charge transport in CNT/FeSe2/C.
g) Nyquist plots and h) Plot of Zre versus ω−1/2 in the low frequency region of CNT/FeSe2, CNT/FeSe2/C-1, and CNT/FeSe2/C-1 anodes, respectively
after 50 cycles.

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the first cathodic sweep, a little reduction peak at ≈1.8 V was
observed which corresponds to the intercalation reaction in the
active material with the formation of NaxFeSe2[26] and subse-
quent to the formation of SEI layer owing to the decomposi-
tion of the electrolyte.[30] Besides, two reduction peaks were also
seen in the first discharge process at approximately 1.02 and
0.51 V, which account for the conversion reaction with the gen-
eration of FeSe, NaSe2, and subsequently Fe and Na2Se, respec-
tively.[18] For the first anodic sweep, three oxidation peaks were
observed at about 1.68, 2.15, and 2.4 V and can be assigned to
the formation of FeSe, the intermediate NaxFeSe, and the final
product FeSe2. Moreover, in subsequent cycles, the CV curves
remain steady and overlap well, indicating that the electrochem-
ical reaction in the hybrid framework remains reversible and
stable. Consistent information as that presented in CV curves
was also harvested from the galvanostatic charge/discharge
voltage curves of the CNT/FeSe2 and CNT/FeSe2/C electrode at
100 mA g−1 (Figure S4, Supporting Information and Figure 4b).
The first cycle process showed the discharge voltage plateaus
located at about ≈1.2 and ≈0.7 V and charge voltage plateaus
located at approximately ≈1.5, ≈2.01, and ≈2.35 V. After the first
cycles, discharge voltage plateaus shifted to higher voltage while
for charge process remain the same. Such a voltage curve was
in good agreement with already reported bulk FeSe2.[27] During
the first discharge and charge process of CNT/FeSe2/C, the spe-
cific capacity was reached to 767 and 548 mAh g−1, respectively,
based on the active mass of the electrode. While, discharge and
charge capacities of CNT/FeSe2/C based on the total mass of
electrode would be 601.4 and 429.3 mAh g−1, respectively.
The large difference in specific capacities for the first cycle
and low initial Coulombic efficiency (71.5%) is attributed to the
formation of SEI film at the electrode/electrolyte interphase and
decomposition of the electrolyte. However, afterward, the Cou-
lombic efficiency is improved to ≈100% (Figure S5, Supporting
Information) as electrode achieved the thermodynamic stability.
It is also observed that discharge capacity difference between
the second and third, third and fourth, fourth and fifth, and so
on is smaller in CNT/FeSe2/C than CNT/FeSe2, which indicates
the advantage of amorphous carbon coating (Figure S4, Sup-
porting Information, and Figure 4b).
Figure 4c shows a comparison of the cycling performance
of pure CNT framework, CNT/C, CNT/FeSe2, CNT/FeSe2/C-1,
and CNT/FeSe2/C-2. After 100 cycles, the discharge capacity
of 546 mAh g−1 was obtained at 100 mA g−1 in case of CNT/
FeSe2/C-1, which is much higher than the pure CNT frame-
work (87 mAh g−1), CNT/C (127 mAh g−1) framework, CNT/
FeSe2 (290 mAh g−1), and CNT/FeSe2/C-2 (471 mAh g−1). The
high cyclic stability of CNT/FeSe2/C-1 is ascribed to the opti-
mized coating of amorphous carbon that not only increases the
electronic conductivity but also buffers the volume expansion
which stabilizes the SEI film without creating barrier to ionic
diffusion during the charging/discharging process. The inferior
performance in CNT/FeSe2 and CNT/FeSe2/C-2 was due to fol-
lowing main reasons: (1) Without amorphous carbon coating
(CNT/FeSe2), the electrode suffers from low electrical conduc-
tivity and excessive side reaction due to direct contact with the
electrolyte, hence irreversible sodium storage and leads to large
volume expansion and capacity fading. However, in the case
of CNT/FeSe2/C-2, the low performance is because of lower
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loading of active materials (FeSe2) in CNT/FeSe2/C-2 compared
with CNT/FeSe2/C-1, sluggish kinetics and elongated diffusion
passage of Na ions in CNT/FeSe2/C-2 due to thick amorphous
carbon coating. Therefore, during the initial electrochemical
process, most of the Na ions entrap in thick carbon shell in
CNT/FeSe2/C-2 composite, which causes lower capacity.
In addition, the theoretical gravimetric capacity (Cg) of CNT/
FeSe2/C electrode is assessed from the theoretical capacity
of FeSe2 (501.5 mAh g−1) and its percentage amount in CNT/
FeSe2/C (78.4 wt%) and capacity of the CNT/C framework
(127 mAh g−1) in present work (Figure 5d) that can be described
as: Cg = 127 × 21.6% + 501.5 × 78.4% = 420.6 mAh g−1. The
capacity achieved in CNT/FeSe2/C composite based on the total
mass is a little larger (428 mAh g−1) than the theoretical cal-
culated capacity of the electrode (420.6 mAh g−1) and thereby
ensuring the high activation or utilization of the active material
(FeSe2) in the composite.
Figure 4d further indicates that CNT/FeSe2/C delivers the dis-
charge specific capacity of 395 mAh g−1 after 200 cycles even at
a high current density of 500 mA g−1 with Coulombic efficiency
of ≈100%. The corresponding charge/discharge voltage profiles
at different cycles indicate the same charge storage behavior
even at high current density (Figure S7, Supporting Informa-
tion). Next, the electrochemical performance of CNT/FeSe2/C
is further assessed by the rate capability test (Figure 4e). The
electrode material was evaluated at various current densities
increasing stepwise from 100 mA g−1 to 1600 mA g−1 and with 7
cycles performed at each step. When the current ramped step-
wise, the final rate capacities of the CNT/FeSe2/C framework
were 544, 501, 407, 314, and 156 mAh g−1 at current densities
of 100, 200, 400, 800, and 1600 mA g−1, respectively. However,
when the current densities are reverted, the discharge capaci-
ties of 259, 371, 463, 532, and 589 mAh g−1 were still obtained at
800, 400, 200, 100, and 50 mA g−1, respectively.
Moreover, a performance comparison of our material is also
carried out with the reported iron selenide based materials as
presented in Table S1, Supporting Information. From Table S1,
Supporting Information, it is clear that our CNT/FeSe2/C
exhibited improved capacitive performance and elongated cyclic
stability up to several hundred cycles compared with any other
reported electrode or comparable with some electrodes.[35–37]
The above-mentioned outcomes show that unique structural
features in CNT/FeSe2/C efficiently improve electrochemical
performance (Figure 4f). For instance, first, the uniformly
embedded FeSe2 NPs into the CNT framework offers numerous
active sites and increases the migration of Na+ ions. Secondly,
interconnected and conductive CNT network provides rapid
and continuous movement of electrons and shortened diffusion
paths for sodium, which in turn increases the charge transfer
process at the electrode/electrolyte interfaces. Third, the outer
amorphous carbon coating on individual FeSe2 NPs enhances
the electronic conductivity of the hybrid, accommodates the
strain-induced during sodium insertion/extraction, inhibits the
agglomeration of FeSe2 NPs, and hinders the corrosion reaction
at FeSe2/electrolyte interfaces. Fourth, the defects present in
the carbon shell may act as additional Na+ storage sites, hence
positively contributing to the capacity. Although, graphitic
carbon layer has been coated over the active materials,[35–36]
which no doubt has benefits in controlling the volume changes
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Figure 5. Electrochemical performance metrics of electrodes with various mass loadings and densities: a) Digital photographs and schematic struc-
tural illustration of the original and densified framework. b) Relation among original thickness, mass loading, and density of CNT/FeSe2/C. c) Areal
capacity at 100 mA g−1 and d) First charge/discharge voltage profiles with mass loading of 6.32, 10.5, and 16.9 mg cm−2. e) Rate capability of CNT/
FeSe2/C with various mass loading.

and side reactions, but suffers from low diffusion of ions. The
keen advantage of the current strategy is coating of amorphous
carbon through a simple process resulting in high ionic dif-
fusivity compared with graphitic carbon or previously coated
materials which is highly required for high performance and
stability.
Furthermore, Nyquist plots of electrodes highlight the advan-
tages of the amorphous carbon coating (Figure 4g). In the high
frequency region, the smaller semicircle for carbon coated elec-
trodes (CNT/FeSe2-1, CNT/FeSe2/C-2) revealed a smaller charge
transfer resistance (Rct) in contrast with the uncoated (CNT/
FeSe2), and hence, it is clear that the carbon coated electrodes
CNT/FeSe2/C possess a better electrical conductivity and reac-
tion kinetics, which is good for enhancing the battery perfor-
mance. The Nyquist plots (Figure 4g) were also deconvoluted
with the equivalent circuit diagram (Figure S8, Supporting
information). Here Rs, Rct, CPE, and Rf display the ohmic
resistance of the electrolyte, charge transfer resistance, constant
phase element (CPE), and SEI film resistance, respectively, in
the high/medium frequency regions. Further, Zw shows the
Warburg impedance in the low frequency region that relates to
the sodium-ion diffusion kinetics used to determine the diffu-
sion coefficient of Na+ ions in the electrodes (in solid).
Z re = Re + Rct + σ ω ω −1/2 (3)
Based on the above equation and through the linear fitting
of Zre verses ω−1/2, the Warburg coefficient (σω) is obtained as
shown in Figure 4h. According to Equation (4), the larger
slope between Zre and ω−1/2 stands for a higher Na+ diffusion
coefficient.[10,24]
DNa = R 2T 2 /2S 2 n 4 F 4CNa
2
σ ω2 (4)
In Equation (4), R is the gas constant, T is absolute tempera-
ture, S is the area of electrodes, n is the electron transfer during
oxidation/reduction process, F is the Faraday constant, and C
is the Na+ ion concentration. The calculated outcomes of DNa
specify that amorphous coated electrodes, (i.e., CNT/FeSe2/C-1
[1.1 × 10−10 cm2 s−1] and CNT/FeSe2/C-2 [5.3 × 10−11 cm2 s−1])
exhibit faster Na+ ion transport than uncoated (CNT/FeSe2
[3.28 × 10−11 cm2 s−1]). These results indicate that amorphous
carbon coating on individual FeSe2 NPs is helpful for rapid
charge transfer process.
Moreover, thinner carbon coated electrode (CNT/FeSe2/C-1)
showed a smaller electronic conductivity than that of thicker
(CNT/FeSe2/C-2) as indicated by a slight larger semi-circle of
CNT/FeSe2/C-1 (Figure 4g), thereby attributed to lower amor-
phous carbon percentage in CNT/FeSe2/C-1 (8.0%) than CNT/
FeSe2/C-2 (17.6%). However, DNA in CNT/FeSe2/C-1 was deter-
mined to be two times higher than that of CNT/FeSe2/C-2
(Figure 4h). Therefore a balanced relationship between the
ionic diffusivity and electrical conductivity is important to
get optimized electrodes and electrochemical performance,
as only higher electronic conductivity does not assure higher
performance.

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For practical applications, high mass loading and density are
required, which can be achieved through a compaction tech-
nique of the 3D framework (Figure 5a).[22] However, it is quite
a big challenge to increase the areal mass loading in the SIBs
for practical applications for bare or NPs-grafted carbon hetero-
structures. Normally, compaction of 3D electrodes to densify
causes sluggish kinetics and poor ionic diffusion, therefore,
ruining the electrochemical performance.[38] Here, three elec-
trodes based on CNT/FeSe2/C framework with different den-
sity and mass loadings were obtained by adjusting the initial
thickness of 2.5, 3.0, and 3.5 mm (Figure 5b). These electrodes
exhibited excellent cyclic stability with good capacity retention
after 50 cycles (Figure 5c). The areal capacity increases linearly
with areal mass loading and attains respective values of 2.72,
4.27, and 5.06 mAh cm−2, which correspond to mass loadings
of 6.32, 10.5, and 16.9 mg cm−2 after 50 cycles. The relation-
ship among initial thickness, areal loading, and areal capacity
is shown in Figure S9, Supporting Information. Moreover,
their charge/discharge voltage profiles are almost the same
(Figure 5d), indicating that the diffusion rate and electro-
chemical storage of Na+ are not affected by the high areal mass
loading. Since the densified framework still maintains the 3D
porous and interconnected network to deliver good electronic
and ionic conductivities. Further, we have calculated the rate
capability of the CNT/FeSe2/C anode at the various areal mass
loading ranging from 6.32 to 16.9 mg cm−2 (Figure 5e). At all
three different areal mass loadings, a good rate performance
was achieved (Figure 5e). Specifically, at very high areal mass
loading of 16.9 mg cm−2, when the specific current density
Figure 6. Quantitative pseudo-capacitive analysis: a,b) CV profiles at various scan rates for CNT/FeSe2/C, and CNT/FeSe2, respectively c) Relationship
between Logarithm scan rate and Logarithm redox peak currents of CNT/FeSe2/C, d) Plots of (scan rate)1/2 verses i (scan rate)−1/2 used to compute con-
stants k1 and k2 at different potentials e) Capacitive contribution at 0.8 mV s−1 scan rate. f) Percentage of capacitive contribution at various scan rates.
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gradually ramped up, areal capacities of 6.11, 5.04, 3.55, 2.58,
and 1.33 mAh cm−2 were reversibly measured at 100, 200, 400,
600, and 800 mA g−1, respectively, where reduction in capacity
is a common trend due to higher current density. However,
when the specific current density reverted to 100 mA g−1, excel-
lent areal capacity retention of 5.26 mAh cm−2 was achieved
demonstrating excellent rate performance of the electrode.
Such good rate performance at ultra-high mass loading is very
important for practical applications such as in high energy and
power density batteries.
In addition, volumetric capacity was calculated based on the
density of the electrodes according to this formula: ρ = m/A × h,
where m, ρ, A, and h are the mass, density, base area, and thick-
ness of the framework, respectively. We obtained volumetric
capacities of 158 mAh cm−3 for the most densified and the
thickest framework corresponding to a density of 528 mg cm−3
(Figure S10, Supporting information). The high areal and volu-
metric capacities are attributed to dual protective carbon net-
work and densified framework.
To understand the better electrochemical properties in
CNT/FeSe2/C compared with CNT/FeSe2, CV curves at dif-
ferent scan rates are performed (Figure 6a,b). It reveals the
same shape during reduction and oxidation processes, but
a peak shift is observed as the scan rate increases, showing
small polarization at higher scan rates. According to previous
reports,[12,39,40] the peak current (i) and scan rate (v) are obeyed
by the Equation i = avb. The value of b is important to deter-
mine the electrochemical behavior (i.e., if b ≈ 0.5, then the
charge storage behavior is dominated by an ionic diffusion
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controlled process and if b ≈ 1.0, it represents a capacitive pro-
cess).[40] The b value for different peaks can be attained by the
slope of the log(i) versus log(v) graph (Figure 6c, Figure S11a,
Supporting Information). Specifically, the contribution of the
capacitive and ionic diffusion at a given potential can be com-
puted via the relationship i(V) = k1v + k2v1/2, where k1v and
k2v1/2 are respectively, the capacitive and ionic diffusion contri-
butions. The k1 and k2 values can be determined by the slope
and intercept of v1/2 verses iv−1/2 plot (Figure 6d, Figure S11b,
Supporting Information). Under the scan rate of 0.8 mV s−1,
the separations of capacitive and ionic diffusion contribu-
tion are presented in Figure 6e and Figure S11c, Supporting
Information, and the share of the capacitive contribution in
the total charge storage of the CNT/FeSe2/C and CNT/FeSe2 is
82% and 78%, respectively, indicating a higher rate capability
in CNT/FeSe2/C than CNT/FeSe2. Moreover, as expected, with
an increasing scan rate, the capacitive contribution increases
gradually for both electrodes (Figure 6f, Figure S11d, Sup-
porting Information).
3. Conclusions
In summary, a cage-on-cage approach is developed for SIB
electrode materials made of the porous CNT/FeSe2/C frame-
work. A simple three-step approach is designed, where ini-
tially Fe2O3 NPs were decorated into the CNT framework
by a simple hydrothermal process, which then successfully
converted into FeSe2 by thermal-induced selenization route
and finally, an amorphous carbon coat is constructed over
each FeSe2 NPs and individual CNT. When used as an anode
for SIB, the CNT/FeSe2/C delivered a reversible gravimetric
capacity of 546 mAh g−1 at 100 mA g−1 after 100 cycles. Even
at a high current density of 500 mA g−1, a discharge capacity
of 423 mAh g−1 is maintained. In addition to the sustained
gravimetric performance, an areal capacity of 5.06 mAh cm−2
was achieved at an ultra-high mass loading (16.9 mg cm−2).
The overall high performance and good stability, including
gravimetric capacity, high material loading, and areal capacity
are attributed to synergistic effects of densely packed structure
and dual conductive carbon network.
4. Experimental Section
Fabrication of CNT/Fe2O3: All the reagents and chemicals were
analytical grade and used without further purification. First, the CNT
framework was synthesized by a CVD method using a precursor solution
containing 1,2-dichlorobenzene as a carbon source and ferrocene as a
catalyst reported by Gui et al.[41] Second, 0.4 m Fe(NO3)3·9H2O and urea
were dissolved in Dimethylformamide (DMF) by magnetic stirring at
room temperature. Then a piece of already fabricated CNT framework
(40 mg) in square shape was immersed into the above solution for
15 min and then transferred into an autoclave for the execution of
hydrothermal reaction at 150 °C for 25 h. After complete reaction, the
hybrid framework was washed many times with deionized (DI) water
and ethanol and subsequently, freeze-dried for further use.
Fabrication of CNT/FeSe2: The CNT/FeSe2 was prepared by the
selenization of CNT/Fe2O3 into the furnace in a reduced atmosphere.
Specifically, the CNT/Fe2O3 framework and Se powder with the ratio
(1:3) were placed in the opposite corner of a glass tube of length 15 cm.
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This glass tube containing the hybrid framework and Se powder was
placed at the center of the furnace tube and selenization was executed at
500 °C for 4 h. under the environment of H2/Ar (15 vol% of H2) gas at a
ramping rate of 10 °C. After selenization, the tube furnace was naturally
cooled down to room temperature and got the product CNT/FeSe2.
Fabrication of CNT/FeSe2/C Framework: The carbon was coated onto
the CNT/FeSe2 framework by a simple carbonization approach. Typically,
the as-prepared CNT/FeSe2 framework was dipped into 0.1 m and
0.2 m aqueous glucose solution (40 mL) in the autoclave to synthesize
CNT/FeSe2/C-1 and CNT/FeSe2/C-2, respectively. The autoclave was
placed in the electric oven for the hydrothermal reaction at 180 °C for
10 h. The glucose coated CNT/FeSe2 was washed several times with DI
water and ethanol and then freeze-dried. Last of all, the glucose coated
CNT/FeSe2 hybrid framework was converted into carbon coated CNT/
FeSe2 framework by an annealing process at 450 °C for 2 h. in an Ar
environment.
Materials Characterizations: The structural and morphological
characterizations of all the frameworks were carried out using SEM
(NOVA SEM) and TEM (FEI Tacnai T20). The crystalline phase
information was observed by a powder X-ray diffractometer (Bruker D8)
using Cu Kα (1.5406 °A) radiation. Raman spectra were recorded via
a Raman microscope (Renishaw) equipped with laser light of 532 nm
wavelength for excitation. The XPS measurements were calculated
on Kratos Axis Ultra monochromatized Al Kα radiation to study the
chemical valence state and surface element composition and chemical
valence of the hybrid. The carbon content in each hybrid framework was
determined by TGA in the air with a heating rate of 10 °C min−1. The
specific surface area and pore size distribution were determined using
the N2 sorption test in the Quantachrome autosorb-IQ gas adsorption
analyzer at 77 K.
Electrochemical Testing: The battery performance was evaluated
using a coin cell CR 2032 battery. The coin cells were manufactured
in the Ar glove box with hybrid frameworks as the working electrode,
and sodium foil as the reference/counter electrode. The working
electrode was used as a free-standing electrode without any passive
components (binders, conductive agent, and current collectors). 1.0 m
NaClO4 in propylene carbonate (PC) = 100 vol% with 5% ethylene
carbonate (EC) was used as the electrolyte, and the glass fiber used
as the separator. The galvanostatic charge/discharge tests were
performed using the LAND CT 2001A analyzer in the voltage range of
0.01–3.0 V. The CV and electrochemical impedance spectroscopy (EIS)
measurements were carried out on an electrochemical work station
(CHI660E).
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Acknowledgements
This work was financially supported by the Key Area R&D Program of
Guangdong Province (2018B030327001, 2018B010109009) and the
Natural Science Foundation of China (51732005, 51772008, 51672007,
and 11974023). Further, the authors would like to acknowledge the
supply of bulk CNT frameworks from Prof. Cao Anyuan’s lab in PKU.
N.M. would like to acknowledge the Vice-Chancellor fellowship scheme
at RMIT University, the RMIT Micro Nano Research Facility (MNRF) in
the Victorian node of the Australian National Fabrication Facility (ANFF),
and the RMIT Microscopy and Microanalysis Facility (RMMF).
Conflict of Interest
The authors declare no conflict of interest.
© 2020 Wiley-VCH GmbH
www.advancedsciencenews.com
Keywords
CNT/FeSe2/C, double cage protection system, free standing electrode,
high areal capacity, sodium ion battery
Received: April 5, 2020
Revised: August 27, 2020
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