Chemical Engineering Journal 366 (2019) 622–630

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Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Carbon-coated mixed-metal sulfide hierarchical structure: MOF-derived T

synthesis and lithium-storage performances
Weiwei Sun1, Xuechun Tao1, Pingping Du, Yong Wang
⁎

Department of Chemical Engineering, School of Environmental and Chemical Engineering, Shanghai University, 99 Shangda Road, Shanghai 200444, PR China

HIGHLIGHTS GRAPHICAL ABSTRACT

• Mixed-metallic MOF is selected to ob-

tain the carbon-coated mixed-metal
MOF-derived approach is used to fabricate the Fe-Zn-involved mixed-metal sulfides with S-doped carbon hollow
microsphere anode, which delivers excellent electrochemical performance for lithium-ion batteries.
sulfide hierarchical structure.
• The Fe-Zn-S@S-doped-C delivers
hollow microsphere morphology of
ultrafine nanoparticles embedded
deeply into carbon matrix.
• The Fe-Zn-S@S-doped-C achieves ex-
tremely large capacities and enhanced
cycling performance.
• Capacitive-controlled lithium-storage
behavior leads to the fast kinetics for
the Fe-Zn-S@S-doped-C composite.

ARTICLE INFO ABSTRACT

Keywords: With the aim to satisfy the demands for future-generation lithium-ion battery (LIB) with large reversible ca-
Metal-organic-framework pacity, high energy density and long-period stability, more explorations focus on the metal sulfide electrode
Hierarchical structure materials. A unique hollow hierarchical sphere of sulfur-doped carbon coated FeS2/ZnS (Fe-Zn-S@S-doped-C) is
Lithium storage demonstrated to be an effective electrode candidate for Li-ion battery in this work. In favor of the robust hollow
Metal sulfide
hierarchically porous spherical structure design, the doped-S in the carbon matrix along with the synergetic
S-doped carbon
effect originated from the two metal sulfide species with different Li-storage potentials, the Fe-Zn-S@S-doped-C
composite exhibits large reversible capacity and long-term stability when utilized as the Li-ion battery anode
material. After 200 cycles, a large capacity (1321 mAh g−1) is retained, which is substantially higher than the
theoretical value of FeS2 or ZnS. The Fe-Zn-S@S-doped-C composite also delivers good rate capabilities (679 and
317 mAh g−1 at 1 and 5 A g−1, respectively). Furthermore, the kinetic analysis based on cyclic voltammograms
and Galvanostatic Intermittent Titration Technique reveal the fast lithium-storage kinetics of the Fe-Zn-S@S-
doped-C electrode, which is largely originated from the dominated pseudocapacitive contribution.

1. Introduction abundant and environmentally friendly, usually possess high theore-

tical capacity and have been purged into more efforts [5–14]. On the
Among the research exploration into the rechargeable lithium-ion basis of the transfer reaction of FeS2 + 4Li+ + 4e− → Fe + 2Li2S, high
batteries (LIBs) [1–4], transitional metal sulfides, which are naturally theoretical capacity has been delivered for the earth-abundant pyrite

⁎
Corresponding author.
E-mail address: yongwang@shu.edu.cn (Y. Wang).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.cej.2019.01.178
Received 13 October 2018; Received in revised form 20 January 2019; Accepted 29 January 2019
Available online 16 February 2019
1385-8947/ © 2019 Elsevier B.V. All rights reserved.
W. Sun, et al.
Scheme 1. Schematic illustration of the preparation process and Li-ion storage properties of hollow Fe-Zn-S@S-doped-C microsphere.
FeS2 (894 mAh g−1). However, poor electrical conductivity and obvious
volume change during cycling result in its poor cycling stability as well
as low rate capability, and further limit the practical application of FeS2
[15–17]. The hybridization of structure-controllable FeS2 with gra-
phene, carbon nanotube, porous carbon and other carbonaceous ma-
terials is an effective method to circumvent the above-mentioned issue
[18–21]. They could deliver shortened diffusion lengths of Li ions,
enhanced electron transport channels, and buffered volume change
along with the lithium intercalation, thus resulting in their improved
electrical conductivity and structural stability during cycling [18–41].
Metal-organic frameworks recently have been adopted as an excellent
template material to fabricate the metal sulfides with carbonaceous
materials via a simple one-step sulfidation process under inert atmo-
sphere [26,27,29]. Furthermore, it is proven that the heterogeneous
metal sulfides, derived from the mixed-metal organic frameworks, can
achieve more active lithium-storage sites and enhanced intrinsic elec-
trical conductivity [42,43]. And the synergetic effect between two or
more metal centers with different Li-storage potentials can further al-
leviate the volume expansion originated from the lithium ion insertion/
extraction, resulting in excellent electrochemical performance [42–45].
In this report, we designed a unique hybrid nanocomposite con-
sisted of hollow sphere-like FeS2/ZnS rooted in porous carbon with S
doping (Fe-Zn-S@S-doped-C). An extremely simple strategy has been
selected, which involved the co-precipitation of the organic ligand (2,
5-dioxido-1, 4-benzenedicarboxylate, DOBDC) and Fe and Zn metal
salts to form a mixed-metallic MOF precursor and the followed one-step
moderated-temperature sulfidation process. The Fe-Zn-S@S-doped-C
composites exhibited extremely large reversible capacity, excellent
cycling stability and rate capability, benefiting from the synergistic
effect between FeS2 and ZnS, the doped S in carbon matrix and the
unique hierarchically porous structure.
2. Experiment
2.1. Preparation of Fe/Zn- MOF-74
In the typical synthesis, Fe(NO3)3·9H2O (0.3636 g), Zn(NO3)2·6H2O
(0.02975 g), DOBDC (0.066 g) and Polyvinylpyrrolidone (0.066 g) were
dissolved in a 15 mL solvent mixture of ethanol, N,N-
Dimethylformamide (DMF) and water with v:v:v = 1:1:1[43]. After
sonicating (30 min) under room temperature, the mixed solution was
stirred at 130 °C for 1 h under single-microwave-irradiation mode with
continuous magnetic (Nova, EU Microwave Chemistry). The product
was washed with ethanol after cooling, and then dried at 60 °C for 12 h
under vacuum; the product of Fe/Zn-MOF-74 (dark-brown) was ob-
tained. Through similar procedures with absence of Zn(NO3)2·6H2O or
Fe(NO3)3·9H2O, respectively, we fabricated single-metallic Fe-MOF-74
and Zn-MOF-74 for comparison.
2.2. Synthesis of Fe-Zn-S@S-doped-C
S powder (upstream side) and the as-prepared Fe/Zn-MOF-74
(downstream side), loaded in a porcelain boat, were annealed under N2
in a tube furnace for 2 h (up to 500 °C; 2 °C min−1). The final product of
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hollow sphere-like Fe-Zn-S@S-doped-C was collected after cooling.
Similarly, FeS2@S-doped-C and ZnS@S-doped-C were also fabricated
by a sulfuration process of Fe-MOF-74 and Zn-MOF-74, respectively.
2.3. Materials characterizations
The product was tested by X-ray diffraction (XRD, RigaKu D/Max-
2550 V, Cu Kα radiation), FE-SEM (JSM-7500F), EDS and TEM (JEO-
JEM-200CX and JEM-2010F). The surface composition of the product
was evaluated by XPS (Phe-SCA-5000). The specific surface and porous
characteristic were performed using a nitrogen adsorption device
(Micromerics ASAP 2020). Netzsch STA 409PG/PC instrument was se-
lected to conduct the TGA measurement. A Renishaw Raman spectro-
meter with the excitation wavelength of 785 nm was selected to char-
acterize the Raman spectroscopay.
2.4. Electrochemical measurements
Active materials (80%), acetylene black (10%), the binder (10%,
PVDF) constitute the working electrode (Loading amount: 1.5 mg cm−2
on copper foil; reference electrode: lithium foil; Electrolyte: 1 M LiPF6
in EC and DEC (1/1, w/w)). Swagelok-type half cells were used to
perform the electrochemical performance at room temperature (25 °C).
The constant current charging-discharging test was carried out on
LAND-CT2001 (voltage range: 0.005–3.0 V). CV and Nyquist diagram
were performed on Autolab PGSTAT101 electrochemical workstation.
3. Results and discussion
The synthetic strategy of Fe/Zn-MOF-74 and derived Fe-Zn-S@S-
doped-C is demonstrated schematically in Scheme 1. Fe/Zn-MOF-74
hollow sphere-like precursor can be fabricated by a one-step microwave
solvothermal reaction among the ferric nitrate, zinc nitrate and the
organic ligand (DOBDC). After sulfuration treatment of Fe/Zn-MOF-74
composite under N2 atmosphere, the mixed metal sulfides trapped in
the S doped carbon matrix (Fe-Zn-S@S-doped-C) is finally obtained. It is
remarkable that the carbon matrix by in-situ growth derived from the
DOBDC ligands can be retained after the one-step direct sulfuration.
The Fe-Zn-S@S-doped-C delivers hollow sphere-like morphology,
which inherits well from the Fe/Zn-MOF-74 precursor. The structure
would endow enhanced lithium insertion/extraction ability to the Fe-
Zn-S@S-doped-C composite.
As indicated in the X-ray diffraction (XRD) results, characteristic
peaks (6.59°, 11.7°, 21.4°, 25.4°, 31.6°, Fig. S1a, Supporting
Information) for the Fe/Zn-MOF-74 precursor agree well with pre-
viously-reported single-metallic Fe-MOF-74 [43]. Besides, Fourier
transform infrared spectroscopy (FTIR) of Fe/Zn-MOF-74 was com-
pared with that for Fe-MOF-74, which delivers similar absorption
peaks. (Fig. S1b, Supporting Information) Two peaks (CeO at
1183 cm−1 and C]O at 1650 cm−1) and the strong peak at 1419 cm−1,
assigning to C]C ring stretching vibrations, confirm the existence of
DOBDC ligands in the structure of Fe/Zn-MOF-74 [43,46,47]. As in-
dicated in the XRD patterns for the Fe-Zn-S@S-doped-C products de-
rived from Fe/Zn-MOF-74 (Fig. 1a), characteristic diffraction peaks at
W. Sun, et al.
Fig. 1. (a) XRD patterns and (b) Nitrogen adsorption-desorption isotherms of Fe-Zn-S@S-doped-C, the insets of (b) show the pore size distributions. (c) Raman spectra
of FeS2@S-doped-C and Fe-Zn-S@S-doped-C. (d) TGA curves of Fe-Zn-S@S-doped-C under air.
28.8°, 33.1°, 37.1°, 40.8°, 47.4°, and 56.3° can be ascribed to the stan-
dard FeS2 (PDF #42-1340), while other peaks around 28.6°, 33.1°,
47.5°, 56.3°, 69.5°, and 76.8° are in good accordance with the standard
ZnS (PDF #05-0566). In the comparative XRD patterns of FeS2@S-
doped-C (Fig. S2, Supporting Information), which was derived from the
single-metallic Fe-MOFs via sulfidation process, only the characteristic
peaks for standard FeS2 (PDF #42-1340) can be observed. As shown in
Fig. S3, Supporting Information the XPS survey spectrum of the Fe-Zn-
S@S-doped-C exhibits the peaks for C 1s, Fe 2p, Zn 2p, and S 2p. Fur-
ther exploration on the high-resolution Fe 2p spectrum (Fig. 2a) in-
dicates the peaks at 720.2 and 707.5 eV, which correspond to the Fe
2p1/2 and Fe 2p3/2 peaks of Fe2+ [29]. Correspondingly, the peaks
assigned to the Zn 2p3/2 and Zn 2p1/2 appear at 1021.3 and 1044.3 eV
in the high-resolution Zn 2p spectrum (Fig. 2b), indicating the existence
of Zn2+ [37]. To explore the interaction between S and C, the high-
resolution S and C spectra are present (Fig. 2c and d). The C-S-C peak
(163.8 eV) detected in S spectrum and the C-S peak (286.5 eV) in C
spectrum, confirm the C and S coupling interaction [29,33,43]. Overall,
the successful synthesis of Fe-Zn-S@S-doped-C composite with the ex-
istence of FeS2, ZnS, and the S-doped carbon matrix have been con-
firmed from the XPS results.
As indicated, the detected Fe, Zn, S and C elements in the EDS curve
(Fig. S4a, Supporting Information) given further evidence for the de-
termination of the composition for the Fe-Zn-S@S-doped-C. The molar
ratio of Fe and Zn can be calculated to be about 9:1, agreeing well with
the experimental values. Comparatively, the existence of Fe, S and C
can be confirmed in the FeS2@S-doped-C composite, on the basic of the
EDS curve (Fig. S4b, Supporting Information). Fig. 1c shows Raman
spectra for Fe-Zn-S@S-doped-C and FeS2@S-doped-C, with the calcu-
lated intensity ratios of D/G peaks (ID:IG) being 1.24 and 1.15, re-
spectively. It indicates the increased number of the defects in Fe-Zn-S@
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S-doped-C with more conductivity, which is propitious to the lithium-
ion diffusion during charge-discharge process [43]. Furthermore, TGA
was conducted on the Fe-Zn-S@S-doped-C under air atmosphere to
explore the carbon and sulfur content (Fig. 1d). Significant weight loss
(51.4%) up to 700 °C can be assigned to the oxidation and gasification
of carbon and doped-S, as well as the transformation of metal sulfide
into metal oxide. Based on the weight loss value and the molar ratio of
metal species from TGA accompanied with EDS results, the carbon
content in Fe-Zn-S@S-doped-C can be calculated to be 28.6%. Fur-
thermore, the doped S in the Fe-Zn-S@S-doped-C composite can also be
estimated to be ∼1.3%, originated from the detected the weight con-
tent of S from the EA results (37.8%) minus the calculated weight
content of S in metal sulfides (36.5%) from the TGA and EDS results.
Based on the N2 absorption isotherm analysis results (Fig. 1b), the Fe-
Zn-S@S-doped-C delivers a specific surface area of about 37.3 m2 g−1.
Besides, the coexistence of micropores and mesopores can be detected
for the Fe-Zn-S@S-doped-C composites, as indicated in the pore size
distribution results (the inset of Fig. 1b). Owing to the large specific
surface area with hierarchical porosity, fast electrolyte migration and
multiple favourable pathways for Li-ion diffusion can be achieved
[28,42,45].
As shown in SEM image for the Fe/Zn-MOF-74 precursor (Fig. 3a),
hollow sphere-like morphology with average size of 200–400 nm can be
detected. After the one-step sulfuration under inert atmosphere, the Fe-
Zn-S@S-doped-C inherits the microsphere morphology with slightly
volume shrinkage and decreased size (100–300 nm, Fig. 3b and c),
originated from the decomposition of MOF precursor. However, the Fe-
Zn-S@S-doped-C microsphere are hollow and with rough surface as-
sembled by particles, as illuminated from SEM image under higher
magnification and TEM images (Fig. 3d–f). It is worth noting that
uniform hollow microsphere morphology cannot be achieved for the Fe-
W. Sun, et al. Chemical Engineering Journal 366 (2019) 622–630

Fig. 2. XPS spectra of Fe-Zn-S@S-doped-C: (a) Fe 2p, (b) Zn 2p, (c) S 2p, (d) C 1s.

Fig. 3. (a) SEM image of Fe/Zn-MOF-74. (b-d) SEM images, (e) TEM image, (f-h) HRTEM images and SAED pattern (the insert of f) and (i-l) elemental mapping
images of Fe-Zn-S@S-doped-C.

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Zn-S@S-doped-C products when the molar ratio of Fe and Zn is
changed. Well-defined diffraction rings can be detected in the SAED
patterns (inset of Fig. 3f), indicating the polycrystalline structure of Fe-
Zn-S@S-doped-C. Furthermore, the FeS2 and ZnS particles (size of
5–10 nm), which embedded in amorphous carbon layer with thickness
in range of 4–6 nm, can be detected in the HRTEM images of the Fe-Zn-
S@S-doped-C (Fig. 3g and h). The lattice fringes (interplanar spacings:
0.271 and 0.163 nm) have be detected, corresponding to the (2 0 0) and
(3 1 1) planes of FeS2 (PDF #42-1340), while the ones of 0.312 and
0.191 nm can be assigned to the (1 1 1) and (2 2 0) planes of ZnS (PDF
#05-0566). The uniformly-dispersed Fe, Zn, S and C can be illuminated
from elemental mapping images, further confirming the composition of
Fe-Zn-S@S-doped-C (Fig. 3i–l). For comparison, the morphologies of
the Fe-MOF-74, Zn-MOF-74 and their derivatives (FeS2@S-doped-C and
ZnS@S-doped-C) were also explored. Sphere-like morphology (dia-
meter: 200–400 nm) of Fe-MOF-74 can be detected in Fig. S5a,
Supporting Information, while the derived FeS2@S-doped-C also de-
livers hollow microsphere morphology with slightly decreased size
(100–300 nm) (Fig. S5b and c, Supporting Information). Besides, the
echinus-like microsphere structure can be observed for the Zn-MOF-74
and its derived ZnS@S-doped-C (Fig. S5d–f, Supporting Information).
The Fe-Zn-S@S-doped-C (main product) and FeS2@S-doped-C,
ZnS@S-doped-C (bench-marked products) were both adopted as anode
materials for LIBs to evaluate their electrochemical performances. The
first-cycle CV curves of Fe-Zn-S@S-doped-C (scan rate: 0.1 mV s−1;
3.0 V–5 mV) deliver a peak at ∼0.65 V in the initial cathodic scan
(Fig. 5a), assigning to the reduction of ZnS to Zn (ZnS + 2Li+ + 2e− →
Li2S + Zn) [38,41], together with the generation of solid electrolyte
interface (SEI) film originated from the irreversible reaction along with
the decomposition of electrolyte. Besides, the sharp cathodic peak ap-
pearing at ∼1.15 V corresponds to the reduction from FeS2 to Li2FeS2
and further to Li2S and Fe (FeS2 + 2Li+ + 2e− → Li2FeS2,
Li2FeS2 + 2Li+ + 2e− → 2Li2S + Fe0) [29,38,41]. During the sub-
sequent anodic scan, a weak anodic peak (∼1.3 V) represents the re-
generation of ZnS from Zn and Li2S (Li2S + Zn → ZnS + 2Li+ + 2e−),
while two peaks at 1.99 and 2.54 V correspond to the multi-step oxi-
dation reactions of Fe and Li2S (2Li2S + Fe0 → Li2FeS2 + 2Li+ + 2e−,
Li2FeS2 Li2−xFeS2 + xLi+ + xe− (0 < x < 0.8)) [27,29]. The un-
observed peak for the formation of Zn-Li alloy from Zn, as well as the
weak reduction and oxidation peaks for ZnS should be ascribed to the
low content of ZnS in Fe-Zn-S@S-doped-C. It is worth noting that the
different lithium-insertion potentials for FeS2 (∼1.15 V) and ZnS
(∼0.67 V) result in the synergistic effect between these two metal
components, that is the inactive component can serve as “volume-buf-
fering reservoir” to alleviate the mechanical stress originated from the
lithium insertion into the active one at a certain potential [29,43]. It
leads to the improved structural integrity and further enhanced cycling
performance of the Fe-Zn-S@S-doped-C electrode. Besides, the first
discharge/charge curves of Fe-Zn-S@S-doped-C at 0.1 C
(1 C = 1000 mA g−1, Fig. 4b), roughly agree with the results of CV. For
comparison, the CV and discharge/charge curves of the benchmarked
FeS2@S-doped-C electrode, as well as the ZnS@S-doped-C electrode are
presented in Fig. S6. As indicated in the cycling performances at 0.1 C
of Fe-Zn-S@S-doped-C and FeS2@S-doped-C electrodes (Fig. 4c), initial
charge/discharge capacities of Fe-Zn-S@S-doped-C can be determined
to be 905/1409 mAh g−1 (Coulombic efficiency: 64%). The significant
loss in the initial capacity is probably originated from the electrolytes
decomposed and unavoidably generated SEI film. After the capacity
decrease for the first 25 cycles, obviously increased reversible capacity
can also be detected for Fe-Zn-S@S-doped-C, which achieves a high
value of 1321 mAh g−1 after 200 cycles. The gradual increased capacity
(after 25 cycles) of Fe-Zn-S@S-doped-C electrode should be assigned to
the activation process associated with the improved Li-diffusion ki-
netics during cycling [27,29,43]. Furthermore, the capacity contribu-
tion of metal sulfides in the Fe-Zn-S@S-doped-C electrode can be de-
termined to be around 1700 mAh g−1 after 200 cycles, based on the
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Chemical Engineering Journal 366 (2019) 622–630
weight percentages of metal sulfides and carbon in the composite. It is
worth noting that the larger-than-theoretical reversible capacities
achieved for Fe-Zn-S@S-doped-C electrode after cycling can be attrib-
uted to its particle-assembled hollow microsphere structure with large
active surface area and more active sites for lithium storage. In addi-
tion, the side reaction like the reversible formation and decomposition
of an organic polymeric/gel-like film from the electrolyte is also ben-
eficial for the extra amount of Li-ion storage capacities [43]. For the
FeS2@S-doped-C electrode, fast capacity fading can be detected with an
extremely lower value (610 mAh g−1) after 200 cycles. Besides, the
cycling performance of the ZnS@S-doped-C electrode has also been
provided, as displayed in Fig. S7. Because the rate stability is also an
important characteristic for the electrode materials of high-perfor-
mance LIBs, the rate capabilities of the Fe-Zn-S@S-doped-C and FeS2@
S-doped-C electrodes has been provided in Fig. 4d. Specific capacities of
800, 735, 679, 510, and 317 mAh g−1 are tested for the Fe-Zn-S@S-
doped-C electrode under 0.2, 0.5, 1, 2, and 5 A g−1, respectively, and a
reversible capacity of 989 mA h g−1 can be retained along with the
current density going back to 0.1 A g−1. As indicated by the Nyquist
plots of Fe-Zn-S@S-doped-C and FeS2@S-doped-C after the first cycle
(Fig. 5e), the Fe-Zn-S@S-doped-C electrode delivers a low charge
transfer resistance (Rct) at the electrode interface with the calculated
value of 151.7 Ω, which is much smaller than that for FeS2@S-doped-C
(258.2 Ω). Due to the impedance spectra can be significant influenced
under different bias voltages applied between cathode and anode, the
EIS measurement under different bias voltages from 0.5 to 2.5 V were
conducted on the Fe-Zn-S@S-doped-C electrode (Fig. 5f). No obvious
differences are detected in the Nyquist plots of the impedance spectra,
demonstrating a rapid transfer speed of Li ions in Fe-Zn-S@S-doped-C
nanocrystals [48]. In addition, the rate capability and the Nyquist plot
of the ZnS@S-doped-C electrode are also provided in Fig. S7.
For fully investigation on the Li-ion storage properties of the Fe-Zn-
S@S-doped-C electrode before and after cycling, CV profiles under
different sweep rates (0.2–0.8 mV s−1) have been conducted and ana-
lyzed [45,49,50]. As the indicated relationship as the following Eq. (1)
(v: scan rate; i: measured current), the b-value of 0.5 corresponds the
diffusion-controlled dynamics, while the b-value of 1 indicates ideal
capacitive-controlled one.
i = av b (1)
For the as-prepared Fe-Zn-S@S-doped-C, the b-values for the anodic
and cathodic peak can be determined to be 0.53 and 0.43, respectively.
The corresponding b-values have increased to be 0.79 and 0.76 for the
cycled Fe-Zn-S@S-doped-C electrode. Besides, the total capacitive
contribution could be determined by the following Eq. (2), in which the
k1v1/2 and k2v represent the diffusion-controlled and capacitive-con-
trolled parts, respectively.
i (V ) = k1 v1/2 + k2 v (2)
Based on these, the contribution of the capacitive capacity for the
Fe-Zn-S@S-doped-C electrode at different sweep rates was determined
(Fig. 5c and d). The Fe-Zn-S@S-doped-C electrode cycled after 200
cycles delivers obviously larger capacitive contribution than the as-
prepared one. Therefore, faster discharge-charge ability can be
achieved for the Fe-Zn-S@S-doped-C electrode after activation, re-
sulting in its gradually increased reversible capacity during cycling.
Capacitive-controlled behavior can be detected for the FeS2@S-doped-C
electrode, however, lower capacitive contribution can be detected for
both this electrode before and after cycling compared to the main
product (Fig. S8, Supporting Information).
Galvanostatic Intermittent Titration Technique (GITT) are also de-
ployed on the Fe-Zn-S@S-doped-C and Fe2S@S-doped-C electrodes to cal-
culate the diffusion coefficients of lithium during cycling according to the
Fick’s second law [45]. (Fig. 6a and b) Obviously, the cycled Fe-Zn-S@S-
doped-C electrode delivers much higher lithium-ion diffusion coefficients
(DLi+) values (1.13 × 10−8 ∼ 6.12 × 10−9 cm2 s−1) than the as-prepared
W. Sun, et al. Chemical Engineering Journal 366 (2019) 622–630

Fig. 4. (a) CV curve and (b) discharge (lithium insertion) and charge (lithium extraction) curves of Fe-Zn-S@S-doped-C for the first cycle. (c) Cycling performances at
0.1 A g−1, (d) rate capability and (e) Nyquist plots for Fe-Zn-S@S-doped-C and FeS2@S-doped-C composites. (f) Nyquist plots of the Fe-Zn-S@S-doped-C under
different voltages for Li-ion batteries.

Fe-Zn-S@S-doped-C (1.06 × 10−9 ∼ 0.87 × 10−12 cm2 s−1). It should be
assigned to the increased active Li-ion storage sites and reduced electrode
polarization for cycled Fe-Zn-S@S-doped-C electrode. For comparison,
much lower lithium-ion diffusion coefficients (DLi+) values
(0.01 × 10−11 ∼ 0.47 × 10−13 cm2 s−1) have been detected for Fe2S@S-
doped-C (Fig. S9, Supporting Information).
Indicated in Table S1 (Supporting Information), the electrochemical
properties comparisons between the hierarchically porous hollow mi-
crosphere electrodes of this work (Fe-Zn-S@S-doped-C) and previous
FeS2 or ZnS related electrodes is present. The achieved large reversible
capacity (1321 mAh g−1 after 200 cycles) for Fe-Zn-S@S-doped-C is
extremely superior to previously-reported various FeS2- or ZnS-based
electrodes. It should be ascribed to synergistic effect between FeS2 and
ZnS as well as the sulfur-doped carbon, especially the MOF derived

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Fig. 5. CV curves with different scan rates of 0.2, 0.4, 0.6, and 0.8 mV s−1, and the linear fit of peak currents versus scan rate and peak currents versus square root of
scan rate: (a) as-synthesized Fe-Zn-S@S-doped-C electrode and (b) Fe-Zn-S@S-doped-C electrode after 200 cycles. The contribution ratio of capacitive and diffusion-
controlled behaviors at different scan rates of (c) as-prepared Fe-Zn-S@S-doped-C electrode and (d) Fe-Zn-S@S-doped-C electrode after 200 cycles.

Fig. 6. (a) Voltage-composition profile discharged from 3 V to 0 V of the as-prepared Fe-Zn-S@S-doped-C and Fe-Zn-S@S-doped-C electrode after 200 cycles in a
GITT mode using an intermittent current rate of C/10 and periodic interruption to reach nearly equilibrium. (b) The calculated lithium-ion diffusion coefficients of
the as-prepared Fe-Zn-S@S-doped-C and Fe-Zn-S@S-doped-C electrode after 200 cycles.

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heterogeneous porous hollow sphere structure. Firstly, the hollow
sphere-like heterogeneous structure and porous characteristics of Fe-
Zn-S@S-doped-C could effectively accommodate the volume expansion
via alleviating the mechanical stress along with the Li-ion insertion/
extraction. Besides, the porous structure along with the existence of S-
doped carbon matrix also allows facilitated lithium ion transportation
and enhanced kinetic rate. In addition, good structural stability can be
achieved for the Fe-Zn-S@S-doped-C electrode, as indicated from its
retained hollow microsphere morphology after 200 cycles (Fig. S10,
Supporting Information). It should be attributed to the MOF derived
porous structure as well as the existence of carbon matrix.
4. Conclusion
In summary, we achieved the synthesis and lithium-ion battery
application of hierarchically porous hollow Fe-Zn-S@S-doped-C mi-
crosphere derived from MOF precursors. The existence of different
metal sulfides, which can react with Li+ under different potentials,
along with the valid confinement by the S-doped carbon matrix, which
also delivers improved electronic and ion transportation, endow the Fe-
Zn-S@S-doped-C electrode with excellent Li-ion storage properties.
Superior cyclability (1321 mAh g−1 after 200 cycles) and high-rate
capability (679 and 317 mAh g−1 at 1 and 5 A g−1, respectively) can be
achieved. The strategy demonstrated here can shed light on the ex-
tended Li-ion battery application for more metal sulfide-based compo-
sites.
Acknowledgments
Weiwei Sun and Xuechun Tao contributed equally to this work. The
authors gratefully acknowledge the financial supports from Shanghai
Municipal Science and Technology Commission (17010500300,
15520720600) and Innovation Program of Shanghai Municipal
Education Commission. The authors also thank Lab for Microstructure,
Instrumental Analysis & Research Centre, Shanghai University for ma-
terials characterization.
Conflicts of interest
There are no conflicts of interest to declare.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cej.2019.01.178.
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