Electrochimica Acta 392 (2021) 139071

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

Synergistic effect between 1T’-ReS2 nanosheet arrays and FeS2

nano-spindle in 1T’-ReS2 @FeS2 @NC heterostructured anode for Na+
storage
Jinyi Lin a, Zilin Peng a, Wei Yang a, Zhiting Liu a, Xinlong Liu a, Rui Sun a, Zhaoxia Qin a,
Haosen Fan a,∗, Yufei Zhang b,∗
a
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China
b
School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China

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

Article history: In this paper, 1T’-ReS2 @FeS2 @NC heterostructure was successfully prepared by growing ReS2 nanosheet
Received 5 June 2021 arrays on porous FeS2 nano-spindle by using metal-organic framework (MIL-88) as precursor. The het-
Revised 2 August 2021
erostructure with external nanosheet array structure ensures sufficient contact between the electrolyte
Accepted 5 August 2021
solution and the electrode material by shortening the ion transfer path. When 1T’-ReS2 @FeS2 @NC het-
Available online 11 August 2021
erostructure was used as anode material of sodium ion battery, it delivered excellent rate performance
Keywords: and cycling stability, reaching a high specific capacity of 729 mAh g−1 at a current density of 0.1
Na+ storage A g−1 . Meanwhile, the results of galvanostatic intermittent titration technique (GITT) and electrochemical
1T’-ReS2 @FeS2 @NC impedance spectroscopy (EIS) tests can indicate that the heterostructure greatly enhances the Na+ dif-
Heterostructure fusion kinetics through combining of three-dimensional porous FeS2 nano-spindle and two-dimensional
Nanosheet arrays nanosheet arrays. It is proved that 1T’-ReS2 @FeS2 @NC heterostructure is a promising anode material for
Nano-spindle
sodium-ion batteries.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction
In recent years, lithium-ion batteries (LIBs) have become the
primary energy source of choice in a variety of portable electron-
ics markets and electric mobility tools markets due to their con-
venience, high energy density and high service life [1-3]. However,
the scarcity and rising price of lithium limit their long-term large-
scale applications which make sodium-ion batteries (SIBs) a poten-
tial candidate for LIBs due to their low cost, abundant resources
and high degree of commercial application [4,5]. However, the Na+
radius is really larger than that of Li+ (1.02 Å for Na+ and 0.76
Å for Li+ ), which does not allow Na+ to be effectively inserted
into the traditional LIBs graphite anode material. It is still a big
challenge to suitable anode material of sodium-ion batteries with
high energy density and high cycle stability [6,7]. Hence, the search
of advanced anode material is one of the main research topics in
sodium ion batteries [8-10].
Recently, Transition metal disulfides (TMDs) are considered as
the promising anode materials of secondary batteries with supe-
rior performance [11]. Compared with the transition metal oxides
∗
Corresponding author.
E-mail addresses: hsfan@gzhu.edu.cn (H. Fan), yfzhang@gdut.edu.cn (Y. Zhang).
(TMOs), the covalent metal-sulfur bond of the transition metal sul-
fide is weaker than that of the metal-oxygen bond [12]. There-
fore, TMDs (especially SnS2 , NiS2 , CoS2 , MoS2 , FeS2 ) are more con-
ducive to conversion reactions, resulting in good electrochemical
activity and cyclic stability for SIBs anode [13-15]. Iron sulfide has
more abundant natural resources and superior electrical activity
[16,17]. However, the large volume expansion may occur during the
charge/discharge process of FeS2 anode, thus affecting its sodium
storage performance [18]. The other transition metal sulfide ReS2
sheet material has anisotropy, high electronic conductivity, and an
open layer structure that can accommodate a large amount of ion
intercalation, the substantial band gap (1.6 eV for ReS2 and 0.95 eV
for FeS2 ) and the incredibly weak Van der Waals force is conducive
to Na+ insertion/extraction [19,20]. ReS2 nanosheets are very easy
to grow on organometallic frameworks and carbon materials, while
being able to maintain structural integrity during using as an elec-
trode material [21]. Von Lim et al. conducted the vertical ReS2
nanoplates uniformly grown on the porous carbon cubes derived
from MOF, which increased the specific surface area and weakened
the volume change set up by the reaction, thereby enabling effi-
cient ion/electron migration. The maximum capacity of this com-
posite material can come to 365 mAh g−1 after 600 cycles under
2 A g−1 [22]. Two different composites of FeS2 /3DG and ReS2 /NTs

https://doi.org/10.1016/j.electacta.2021.139071
0013-4686/© 2021 Elsevier Ltd. All rights reserved.
J. Lin, Z. Peng, W. Yang et al. Electrochimica Acta 392 (2021) 139071

Fig. 1. Schematic illustration displaying the fabrication procedure of 1T’-ReS2 @FeS2 @NC heterostructures.

were successfully prepared by hydrothermal synthesis and used as The brick-red MIL-88 precipitate was obtained by centrifugation
electrochemical capacitor electrode materials [23]. The composites and washed twice with deionized water and ethanol, respectively.
show a specific capacitance of ≈110 F g−1 for ReS2 /7 wt% NTs at The precipitate was then dried in a vacuum oven at 60°C for 12 h.
0.2 A g−1 and 240 F g−1 for 3DG/15 wt% FeS2 . Hence, Iron and rhe-
nium sulfides present great potential as anodes for sodium-ion bat-
teries. Therefore, preparation of heterogeneous structures of ReS2 2.2. Preparation of FeS2
and FeS2 may be an effective method to improve the sodium ion
storage property. However, there is rare report about the hybrid To synthesis porous FeS2 nano-spindle, MIL-88 powder and sul-
materials of iron sulfide and rhenium sulfides being used as anode fur powder were mixed in the ratio of 1:2 by mass. The powder
materials for SIBs. mixture was heated at 550°C for 2 h in a tube furnace under a
Recently, the metal-organic framework (MOF) hybrid material nitrogen atmosphere by increasing temperatures at a rate of 3°C
with a porous structure is widely applied as precursors for the min−1 . Then, the product was naturally cooled to room tempera-
preparation of nanostructured materials [24-26]. Herein, inspiring ture.
from the synergistic effect of iron sulfide and rhenium sulfide, we
have prepared 1T’-ReS2 @FeS2 @NC heterostructure from growing
ReS2 nanosheet arrays on the surface of FeS2 nano-spindle by us-
2.3. Synthesis of 1T’-ReS2 @FeS2 @NC
ing iron-containing MOF (MIL-88) as the iron source and precursor
(Figure 1). After sulfidation in a tube furnace, the ReS2 nanosheets
0.03 g of FeS2 powder, 0.067 g of ammonium perrhenate
were uniformly grown to form 1T’-ReS2 @FeS2 @NC heterostructure.
(NH4 ReO4 ), 0.094 g of thiourea (CS(NH2 )2 ) and 0.042 g of hy-
This special 2D-3D heterostructure provides large specific surface
droxyammonium chloride (NH2 OH-HCl) were mixed with 40 ml of
area and stable structure, which effectively facilitate the Na+ diffu-
deionized water. The mixture was dispersed in an ultrasonic appa-
sion and charge transfer, as well as maintain the whole structural
ratus for at least 1 h and then placed in a Teflon autoclave. The
integrity by suppressing the volume expansion of the electrode
autoclave was heated in a programmed oven at 220°C for 20 h. Fi-
material. At last, the 1T’-ReS2 @FeS2 @NC heterostructure manifests
nally, the product was washed 3 times with water and ethanol and
fantastic electrochemical performance, including outstanding rate
then dried by a vacuum oven at 60 °C for 12h.
capacity, excellent cycling stability and superior capacitive contri-
bution.

2.4. Materials characterization

2. Experimental section
2.1. Preparation of MIL-88 precursor
In a typical step, fumaric acid (0.232 g) and Fe(NO3 )3 •9H2 O
(0.606 g) were added to 40 mL of N,N-dimethylformamide by a
simple one-step method and dissolved with thorough stirring, then
the resulting mixture was transferred into a 50 mL Teflon auto-
clave. The autoclave was heated at 120°C for 2 h in a blast Oven.
The sample was characterized by scanning electron micro-
scope (SEM JEOL JEM-7001F), energy dispersive X-ray spectroscopy
(EDS OXFORD, Ultim Extreme), transmission electron microscope
(TEM JEOL JEM-2100F), X-ray diffraction (Panalytical PW3040/60,
Cu Kα radiation, λ=1.5418 Å), X-ray Photoelectron Spectroscopy
(XPS ThermoFischer ESCALAB Xi+, monochromatic Al-Kα radia-
tion (hυ =1486.6 eV)) and automatic physical adsorption instru-
ment (BET Micromeritics ASPA2020, 2460-N2 ).

2
J. Lin, Z. Peng, W. Yang et al.
Fig. 2. SEM of (a) MIL-88, (b) FeS2 and (c-d) 1T’-ReS2 @FeS2 @NC. (e) TEM and (f) HRTEM of 1T’-ReS2 @FeS2 @NC. (g-k) element mapping of 1T’-ReS2 @FeS2 @NC heterostructure.
2.5. Electrochemical measurements
The electrochemical performance of 1T’-ReS2 @FeS2 @NC mate-
rials as sodium-ion half-battery anodes was tested by assembling
them into CR2032 button batteries. In this experiment, the copper
foil was used as the anode current collector for the sodium-ion
battery. The active substance, acetylene black, and sodium alginate
were mixed in a mass ratio of 7:2:1, and the appropriate amount
of deionized water was added dropwise to grind and stir into a
slurry. After that, the slurry is evenly applied to the copper foil and
heated under a vacuum oven at 80°C for at least 12 h. The assem-
bly of the button battery is carried out in a glove box filled with ar-
gon gas. The oxygen concentration and water concentration in the
glove box are controlled to be within 1 ppm. The electrolyte used
for the button battery was 1 M NaClO4 (EC/DEC=1:1) solution, and
glass fiber was used as the button battery separator, while the
sodium block was cut to a suitable size as the reference electrode.
The charge/discharge test and GITT test are conducted through the
NEWARE battery testing station, with a voltage window of 0.01-3
V. Cyclic voltammetry (CV) and electrochemical impedance spec-
troscopy tests are performed in the IVIUM electrochemical work-
station, and the electrochemical impedance spectroscopy test fre-
quency was 0.01-10 0 0 0 0 Hz.
3. Result and discussion
The scanning electron micrograph (SEM) image of the MIL-88
precursor is displayed in Figure 2a, which exhibits a spindle-like
structure with an average length of 60 0-80 0 nm and an average
width of 100-150 nm. After sulfidation process, the surface of the
FeS2 nano-spindles becomes rough and the particles become loose
and porous, and this structure is more favorable for electron/ion
transport (Figure 2b). After the growth of ReS2 nanosheets by hy-
drothermal method, as shown in Figure 2c-d, 1T’-ReS2 @FeS2 @NC
heterostructure with porous FeS2 nano-spindle in the interior and
vertically interlaced ReS2 nanosheets in the exterior was success-
fully prepared, in which the thickness of ReS2 nanosheets is about
10-20 nm. Such novel hierarchical structure can effectively increase
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Electrochimica Acta 392 (2021) 139071
specific surface area and provide more active sites, which is more
favorable to facilitate the Na+ ion diffusion and accommodate the
volume expansion during the charge/discharge cycle of the battery.
The final sample has a specific surface area of 29.62 m g−1 and a
highly porous structure with a wide range of pore sizes from 2-
10 nm (Fig.S1). Meanwhile, more details of the nanostructure can
be seen from TEM and HRTEM, and the sheet structure of the par-
ticle surface can be clearly seen in Figure 2e. The high magnifi-
cation details of the material are observed at the junction of the
nanosheets and particles. As shown in Figure 2f, we can see visi-
ble lattice stripes. The lattice spacings of 0.304 nm and 0.258 nm
marked by yellow arrows in the figure correspond to (2 0 0) and
(2 -2 1) crystal planes of ReS2 , while the lattice spacings of 0.242
nm and 0.271 nm marked by blue arrows correspond to (2 1 0)
and (2 0 0) crystal planes of FeS2 , respectively. Further, elemental
mapping analysis (Figure 2g-k) demonstrates that Fe, Re, C and S
elements are evenly distributed into the whole 1T’-ReS2 @FeS2 @NC
heterostructure.
The X-ray diffraction (XRD) pattern of 1T’-ReS2 @FeS2 @NC is dis-
played in Figure 3a. The spectra show characteristic diffraction
peaks at Bragg angles (2θ ) of 14.5°, 37.9°, and 44.6°, correspond-
ing to the (1 0 0), (1 0 2), and (3 -1 1) crystal planes of 1T’-ReS2
(PDF# 82-1379). The characteristic diffraction peaks exhibited at
Bragg angles (2θ ) of 33.0° and 37.0° correspond to the (2 0 0) and
(2 1 0) crystal planes of the FeS2 pattern (PDF# 71-2219), which
correspond to the lattice stripes exhibited in Figure 2f. The appear-
ance of distinct lattice stripes on each side of the contact surface
indicates that the ReS2 nanosheets and FeS2 are well bonded. The
sample was analyzed by X-ray photoelectron spectroscopy (XPS)
for valence studies, which further confirmed the structural com-
position of 1T’-ReS2 @FeS2 @NC. Figure 3b illustrates the XPS sur-
vey spectrum of 1T’-ReS2 @FeS2 @NC, which proved that the ele-
ment peaks of Re, S, C, and N can be detected. Unfortunately, the
elemental peaks of Fe derived after scanning are not obvious, yet
Fe is detected in both the Mapping analysis and XRD spectra of
the elements from Figure 2i and Figure 3a. Besides, the EDS spec-
trum of the final sample illustrates that Fe can be detected (Fig.S2).
Therefore, the reason for the non-detection of Fe peaks in the XPS
J. Lin, Z. Peng, W. Yang et al.
Fig. 3. (a) XRD pattern and standard PDF data of 1T’-ReS2 @FeS2 @NC. (b) XPS survey spectra of 1T’-ReS2 @FeS2 @NC. (c) XPS Re 4f spectra; (d) XPS S 2p spectra. (e) XPS C 1s
spectra. (f) XPS N 1s spectra.
spectra is most likely that the ReS2 on the surface hinders the de-
tection of internal FeS2 by X-rays. The two distinctive characteristic
peaks exhibited at 42.1 eV and 44.5 eV correspond to the energy
peaks of Re 4f5/2 and Re 4f7/2 , respectively [27,28]. As displayed in
Figure 3d, two characteristic peaks located at 162.2 eV and 163.4
eV for the bonding configurations of sulfur are detected, corre-
sponding to S 2p3/2 and S 2p1/2 [27,29]. Besides, the peak at 168.9
eV is most possibly caused by the partial oxidation of the sulfide
surface. The high-resolution C 1s XPS spectrum can be assigned to
a delocalized sp2-hybridized carbon atoms with binding energy of
284.5 eV and a carbon-nitrogen bond with binding energy of 285.6
eV (Figure 3e). Figure 3f exhibits the high-resolution XPS spectrum
of N 1s with two peaks at approximately 399.6 eV and 401.7 eV
corresponding to pyrrolic nitrogen and classic graphitic-type qua-
ternary nitrogen, respectively.
The cyclic voltammetry curves (CV) for the first 5 cycles at a
scan rate of 0.1 mV s−1 in the voltage window of 0.01-3.0 V are
displayed in Figure 4a. It can be seen that there is a clear peak at
0.89 V in the first cycle, which is a reduction peak due to the so-
diation process of the battery and the generation of a stable solid
electrolyte interface (SEI). In the second and subsequent cycles, for
ReS2 , the reduction peak appearing at 1.65 V can be explained by
generating Re and amorphous Na2 S. A clear oxidation peak near
2.1 V corresponds to the desodiation process of Re, implying the
reformation and further oxidation of ReSx [30]. Similar to FeS2 , a
distinct peak around 1.35 V corresponds to the generation of FeSx ,
and the reduction peaks at 0.44 V and 1.84 V can be interpreted
as the conversion of the sodiation process of FeSx to Fe and amor-
phous Na2 S [31]. The plateau of the discharge curve in the first 5
cycles of the constant current charge-discharge curve (Figure 4b)
at a current density of 0.1 A g−1 is similar to the CV peak around
0.98 V in the first cycle of the curve corresponds to each other.
The first cycle is capable of reaching a discharge specific capacity
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Electrochimica Acta 392 (2021) 139071
of 940 mAh g−1 , while the initial discharge loss generated in the
first cycle can be explained by the electrolyte decomposition and
the irreversibility of the SEI film. The following cycle curves over-
lap fundamentally, indicating good cycle reversibility.
The charge storage performance at different current densities
is shown in Figure 4c. Specific capacities of 686, 618, 561, 509, and
417 mAh g−1 were obtained at current densities of 0.2, 0.5, 1.0, 2.0,
and 5.0 A g−1 , respectively. A high specific capacity of 729 mAh
g−1 was even achieved at a current density of 0.1 A g−1 . In compar-
ison, the rate performance of 1T’-ReS2 @FeS2 @NC is superior at all
current densities. Figure 4d shows the charge/discharge curves of
the sodium-ion battery at different densities of 1T’-ReS2 @FeS2 @NC,
which further illustrates the excellent specific capacity perfor-
mance of the battery. The cycling performance of FeS2 , pure ReS2,
and 1T’-ReS2 @FeS2 @NC at the current density of 0.5A g−1 is shown
in Figure 4e. 1T’-ReS2 @FeS2 @NC exhibits a higher specific capac-
ity at the same current density. Moreover, at a current density of
1.0 A g−1 , 1T’-ReS2 @FeS2 @NC is stable for 300 cycles, suggesting
that the material has good cycling stability (Figure 4f). Compared
with other previously reported electrode materials for sodium ion
batteries associated with FeS2 or ReS2 , 1T’-ReS2 @FeS2 @NC outper-
forms most other anode materials (Figure 4g) [13,22,29-34].
To further demonstrate the electrochemical performance of 1T’-
ReS2 @FeS2 @NC as sodium-ion battery anode, the capacitance char-
acteristics were tested with CV curves at different scan rates of
0.1, 0.3, 0.5, 0.8, and 1.0 mV s−1 for further battery kinetic anal-
ysis (Figure 5a). The CV peaks expand outward as the scan rate
becomes larger, which is due to the electrode polarization at differ-
ent current densities. The shape of the CV curves at each scan rate
is very similar, which proves that the battery has good cycling sta-
bility. The peak current i also becomes larger during the increase
of the scan rate. However, the peak current i is not proportional to
the square root of υ , indicating that the electrochemical behavior
J. Lin, Z. Peng, W. Yang et al. Electrochimica Acta 392 (2021) 139071

Fig. 4. (a) CV curves of 1T’-ReS2 @FeS2 @NC with the scan rate of 0.1 mV s−1 . (b) Charge/discharge curve for the first 5 cycles at a current density of 0.1 A g−1 . (c) Rate
performance of the FeS2 , 1T’-ReS2 @FeS2 @NC and pure ReS2 electrodes at different current densities. (d) Charge/discharge profiles of 1T’-ReS2 @FeS2 @NC at different current
densities. (e) Comparison of the cycling stability of FeS2 , 1T’-ReS2 @FeS2 @NC, and pure ReS2 at a current density of 0.5 A g−1 . (f) Cycling stability of 1T’-ReS2 @FeS2 @NC at a
current density of 1.0 A g−1 . (g) Comparison of relevant literature on electrode materials for sodium-ion batteries.

Fig. 5. (a) Cyclic voltammograms of the 1T’-ReS2 @FeS2 @NC electrode at different scan rates from 0.1 to 1.0 mV s−1 . (b) Log(i) versus log(υ ) plot for each peak and the slope
of the fitted line. (c) The contribution of the capacitance control charge at different scan rates. (d) Cyclic voltammogram showing the capacitive contribution fraction at
1.0 mV s−1 .

5
J. Lin, Z. Peng, W. Yang et al.
Fig. 6. (a) Discharge and charge curves of the GITT test during the first cycle for the 1T’-ReS2 @FeS2 @NC electrode. (b) The detailed voltage response of the 1T’-ReS2 @FeS2 @NC
electrode during a single current pulse for 10 min followed by an open-circuit stand for 30 min. Chemical diffusion coefficients of Na+ in the 1T’-ReS2 @FeS2 @NC electrode
during the first discharge and charge process.
of the battery is controlled by both capacitive and battery behavior.
The 1T’-ReS2 @FeS2 @NC charge storage mechanism can be quanti-
tatively evaluated from Equation 1 [35].
log (i ) = b log(υ ) + log(a )
Taking a and b as empirical constants, a linear fit to the peak
current i and scan rate υ yields the slope as the b value. As shown
in Figure 5b, the b values of each peak are obtained after fitting
as 0.962, 0.977, 0.940, 0.804, 0.974. b values can determine the ki-
netic process of sodium transfer during charging and discharging,
and the b values of each peak are close to peak 1, so the capacitive
behavior plays a dominant role in the kinetic process of charging
and discharging. We can quantify the battery contribution and the
capacitance contribution using Equation 2, where the capacitance
contribution (surface control) and the battery contribution (diffu-
sion control) are represented by k1 υ and k2 υ , respectively.
i(V )/ υ 1/2 = k1 υ 1/2 + k2
The capacitance contributions at different scan rates are sum-
marized in Figure 5c, where the capacitance contributions are
75.59%, 81.35%, 85.46%, 87.54%, and 91.23% at the scan rates of 0.1,
0.3, 0.5, 0.8, and 1.0 mV s−1 , respectively. The results show that
the reason for the high-rate performance of the battery is the high
capacitance contribution, which can even reach 91.23% at a scan
rate of 1.0 mV s−1 (Figure 5d). The high capacitance and high-rate
performance of the battery are attributed to the rough surface and
sheet structure of the material, which greatly increase the specific
surface area and thus accelerate the Na+ transport and the electro-
chemical reaction on the surface.
Electrochimica Acta 392 (2021) 139071
For the further exploration of the specific rate properties in the
electrode materials, the galvanostatic intermittent titration tech-
nique (GITT) was used to explore the Na+ diffusion behavior. The
(1) response of each time-dependent voltage is obtained after apply-
ing a stabilized current pulse of 30 minutes to the electrode with
a current density of 100 mA g−1 followed by a relaxation time of
60 minutes in this experiment. The diffusion coefficient of Na+ can
be quantified according to the following Equation 3: [36]
4 mVM 2 Es 2
DN a+ = ( ) ( ) (3)
π τ MA E τ
In the equation, τ denotes the current pulse time, m and M re-
spectively denote the mass and molar mass of the material. A is
used to represent the surface area of the electrode, and VM repre-
sents the molar volume of the electrode material. The steady-state
voltage changes and the plateau voltage change generated before
(2) and after the pulse are denoted by Es and Eτ . Figure 6a exhibits
the overall GITT response plot of voltage versus time formed un-
der a constant current pulse. From the local voltage response plot
shown in Figure 6b, it can be seen that the application of a con-
stant current pulse causes a jump in voltage (iR drop) followed by
a slow drop (࢞Eτ ) thus maintaining an equilibrium concentration
gradient. After ceasing the constant current pulse, the relaxation
time begins. At this point, the voltage jumps up (IR drop) and the
Na+ diffusion during the subsequent rise (Es ) makes the entire
chemical composition homogeneous once again. The Na+ diffusion
diagram of the discharge process (Figure 6c) reveals that the dif-
fusion process is a dynamical change process. The diffusion at the
6
J. Lin, Z. Peng, W. Yang et al.
Fig. 7. (a) Nyquist plots and fitted curves of 1T’-ReS2 @FeS2 @NC, FeS2, and pure ReS2 (equivalent circuits were inserted). (b) After the 10th cycle, FeS2 , 1T’-ReS2 @FeS2 @NC, and
pure ReS2 electrodes were line fitted in the real part of the Nernst plot. (c) SEM image of 1T’-ReS2 @FeS2 @NC after cycling. (d) Schematic diagram of the sodiation/desodiation
process 1T’-ReS2 @FeS2 @NC heterostructure.
beginning is a jump plateau to a minimum value at 0.39 V, sug-
gesting that Na+ undergoes a phase change at this point, which
can correspond to a resistance to the diffusion of Na+ due to the
gradual generation of Na2 S. Afterward, Na2 S is completely gener-
ated and the diffusion rate starts to recover. Similarly, during the
charge process (Figure 6d), a jump in the diffusion curve means a
change in the Na phase state and the diffusion coefficient needs to
be reduced appropriately to overcome the resistance of the diffu-
sion process. The point where the diffusion coefficient decreases in
the Na+ diffusion diagram for the charging and discharging process
can roughly correspond to the position of the peak of the CV [37].
The electrochemical impedance spectroscopy provides further
insight into the reaction kinetics of the battery. Figure 7a shows
the Nyquist curves and fitted curves for 1T’-ReS2 @FeS2 @NC-0th
(before cycling), 1T’-ReS2 @FeS2 @NC-10th (after 10 cycles), FeS2 -
10th , and pure ReS2 -10th . The curve consists of a semicircle at
the high-frequency region associated with charge transfer and a
sloping line at the low-frequency region related to Na+ diffusion.
The curves illustrate the presence of both electrochemical polar-
ization processes and concentration polarization processes at the
electrode. In the equivalent circuit model inserted in Figure 7a, Rs
represents the internal resistance of the electrode and electrolyte,
and the double layer capacitance CPE1 is mainly caused by the in-
active ions in the electrolyte. Rct represents the Faraday impedance
caused by the active ions in the electrolyte, where the redox re-
action occurs. W1 represents the Warburg impedance caused by
the diffusion. The diameter of the 1T’-ReS2 @FeS2 @NC curve after
cycling is smaller than that of FeS2 and pure ReS2 , which means
that the impedance of the former is smaller. The resistance of
1T’-ReS2 @FeS2 @NC after cycling is smaller than that before cy-
cling, demonstrating that the SEI film produced by the electrode
7
Electrochimica Acta 392 (2021) 139071
activation enhances the electrical conductivity of the material.
Figure 7b represents the Z’-ω−1/2 plotting for the low-frequency
part (ω = 2π f), and the slope of the straight line after passing
the fit is the Warburg coefficient σ , which is negatively correlated
with the ion diffusion coefficient DNa + . From the Figure 7b, it can
be obtained that the slope of the straight line for FeS2 @ReS2 -10th
is smaller than those of FeS2 -10th and pure ReS2 -10th , indicating
a high diffusion rate for the 1T’-ReS2 @FeS2 @NC. The active mate-
rial after cycling is shown in Figure 7c. The obvious lamellar struc-
ture of 1T’-ReS2 @FeS2 @NC can still be seen on the surface after cy-
cling, which illustrates that the material presents good structural
integrity. The vertical sheet structure on the surface is beneficial
for the electrolyte to fully contact with the electrode and acceler-
ate the insertion/extraction of Na+ . Figure 7d presents the possible
insertion process of Na+ into the 1T’-ReS2 @FeS2 @NC heterostruc-
ture. At a result, particles with structural integrity not only prevent
the stacking of nanosheets on the surface but also provide buffer
space for material expansion. All these advantages provide a great
benefit for the high-performance characteristics of the material.
4. Conclusion
In conclusion, we have successfully synthesized 1T’-
ReS2 @FeS2 @NC heterostructures through growing ReS2 nanosheet
arrays on the surface of FeS2 nanos-spindle by MOF-templated and
subsequent hydrothermal method. The vertical ReS2 nanosheet
arrays on the surface of FeS2 nanos-spindle provides large specific
surface area and more active sites, which improve the sodium ion
transport kinetics. Meanwhile, the combination of 3D FeS2 nanos-
spindle and 2D ReS2 nanosheet arrays greatly helps to maintain
the structural integrity and provides sufficient buffer space for the
J. Lin, Z. Peng, W. Yang et al.
material expansion during the repeated charge/discharge process.
When evaluated as anode materials of SIBs, 1T’-ReS2 @FeS2 @NC
electrode displays better Na+ storage performance than those of
pure FeS2 and ReS2 electrodes, exhibiting a high capacity of 729
mAh g−1 at a current density of 0.1 A g−1 . Thus, it is illustrated
that 1T’-ReS2 @FeS2 @NC heterostructures is a promising anode
material for sodium-ion batteries with broad research prospects.
This experiment also provides a new design method for the
construction of novel multiple metal sulfides hybrid in the field of
energy storage and conversion.
Credit author statement
Jinyi Lin: Data curation, Writing original draft.
Zilin Peng, Wei Yang and Zhiting Liu: Investigation.
Xinlong Liu, Rui Sun and Zhaoxia Qin: Formal analysis.
Haosen Fan: Supervision, Writing-review & editing.
Yufei Zhang: Supervision, Methodology, Writing-review & edit-
ing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
Supplementary materials
Supplementary material associated with this article can be
found, in the online version, at doi:10.1016/j.electacta.2021.139071.
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