Journal of Power Sources 455 (2020) 227937

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Journal of Power Sources

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

MOF derived ZnSe–FeSe2/RGO Nanocomposites with enhanced sodium/

potassium storage
Jujun Yuan a, 1, Wen Liu b, 1, Xianke Zhang a, Yaohui Zhang c, **, Wentao Yang b, Weidong Lai a,
Xiaokang Li a, Jiujun Zhang b, d, Xifei Li b, e, *
a
School of Physics and Electronics, Gannan Normal University, Ganzhou, 341000, PR China
b
Xi’an Key Laboratory of New Energy Materials and Devices, Institute of Advanced Electrochemical Energy & School of Materials Science and Engineering, Xi’an
University of Technology, Xi’an, Shaanxi, 710048, PR China
c
School of Physics, Harbin Institute of Technology, Harbin, Heilongjiang, 150001, PR China
d
Institute for Sustainable Energy, Shanghai University, Shanghai, 200444, PR China
e
Center for International Cooperation on Designer Low-carbon & Environmental Materials (CDLCEM), Zhengzhou University, Zhengzhou, Henan, 450001, China

A R T I C L E I N F O A B S T R A C T

Keywords: ZnSe–FeSe2/reduced graphene oxide (RGO) composites are synthesized through a rational strategy using Fe/Zn-
ZnSe-FeSe2/RGO nanocomposites MOF-5 as a template. Compared with the ZnSe/RGO or FeSe2/RGO composites, the ZnSe–FeSe2/RGO anode
Anode material electrode exhibits a higher reversible capacity (439 mAh g 1 after 100 cycles at 100 mA g 1) for sodium ion
Sodium ion batteries
batteries (SIBs). The excellent electrochemical performance of ZnSe–FeSe2/RGO composites can be attributed to
Potassium ion batteries
Fe/Zn-MOF-5 template
the synergistic effects of the unique architecture, where ZnSe is responsible for providing a high capacity, FeSe2
improves the electrochemical stability, and RGO is beneficial for enhancing the charge transfer behavior.
Furthermore, the ZnSe–FeSe2/RGO anode reveals stable reversible capacity (363 mAh g 1 after 100 cycles at 50
mA g 1) for potassium ion batteries (KIBs).

1. Introduction environmental friendliness [13–21]. For example, Fe7Se8@C nanorods

As a green and effective energy storage device, lithium-ion batteries
(LIBs) have been successfully applied to the fields of portable electronics
and electric vehicles [1–5]. However, the limited lithium salt resources
and its high price have been an obstacle for large-scale energy storage. In
contrast to LIBs, SIBs [6–8] and KIBs [9,10] have received considerable
attention owing to abundant resources of sodium (potassium) and their
similar electrochemical principles with LIBs. However, compared with
the radius of Liþ (0.76 Å), Naþ(Kþ) shows larger radius of 1.09 Å (1.38
Å), which will lead to a larger volume variation and severe structure
pulverization of electrode materials during the charge/discharge pro­
cesses. Therefore, developing effective electrode materials for NIBs
(KIBs) has been challenging [11,12].
Recently, metal selenide-based electrode materials (MxSey, M ¼ Fe,
Zn, Co, Mo, Sn, Sb) have been reported as promising anodes of NIBs
(KIBs) owing to their high capacity, chemical stability, and
anode displayed a stable capacity of 360 mAh g 1 after 100 cycles at
300 mA g 1 for SIBs anode [14]. For the ZnSe microsphere/CNT com­
posites, it delivered the capacity of 362 mAh g 1 at 200 mA g 1 after 80
cycles [15]. Amazingly, the CoSe2/carbon nanofiber as an SIBs anode
showed a high reversible capacity (371.8 mAh g 1 at 200 mA g 1) [17].
In addition, MoSe2/N-doped carbon exhibited 258 mAh g 1 after 300
cycles at 100 mA g 1 [19] when used as KIBs anode. Although attractive
results of metal selenide materials were previously reported, how to
further enhance the battery performance of anode materials has been
challenging since the electrochemical conversion and alloying reactions
are usually accompanied by large volume variation and continuous
growth of solid electrolyte interface (SEI) films.
To address this barrier, great effects have been devoted by designing
the composites of mixed-metal selenide and conductive carbon for
improving the electrochemical performance of energy-related devices
[22–27]. Particularly, two different metal cations in the mixed-metal

* Corresponding author. Xi’an Key Laboratory of New Energy Materials and Devices, Institute of Advanced Electrochemical Energy & School of Materials Science
and Engineering, Xi’an University of Technology, Xi’an, Shaanxi, 710048, PR China.
** Corresponding author.
E-mail addresses: hitcrazyzyh@hit.edu.cn (Y. Zhang), xfli2011@hotmail.com (X. Li).
1
Authors Jujun Yuan and Wen Liu make the same contribution to this work.

https://doi.org/10.1016/j.jpowsour.2020.227937
Received 6 January 2020; Received in revised form 16 February 2020; Accepted 21 February 2020
Available online 5 March 2020
0378-7753/© 2020 Elsevier B.V. All rights reserved.
J. Yuan et al.
Scheme 1. Scheme illustration of the synthesis procedures of ZnSe–FeSe2/RGO composites.
selenide act as buffer matrix each other due to their different reaction
potential during charge-discharge processes, which can relieve the stress
of Naþ/Kþ insertion [22,24]. So far, mixed-metal selenide micro/nano
structures have been synthesized by different strategies including hy­
drothermal method [28,29], solvothermal method [30], and
template-assisted synthesis [23,25,26,31] etc. With these strategies,
metal-organic frameworks (MOFs) were proved as effective templates to
obtain various mixed-metal selenide materials for SIBs anode with
excellent performance because of their tunable architecture and chem­
ical constituents [23,25,26]. For instance, CoSe2/(NiCo)Se2 hollow
nanocube derived from zeolitic imidazolate framework-67 exhibited
enhanced electrochemical property for the SIB anode [23]. The fabri­
cation of CoSe2/ZnSe nanoflakes using CoZn-MOFs nanoflakes as tem­
plates also showed excellent sodium storage capability [26].
Furthermore, RGO (reduced graphene oxide) has been considered as an
ideal 2D matrix for electron/ion transport [32–34]. When combined
with mixed-metal selenide materials for NIBs (KIBs) anode, RGO can act
as a conductive network to enhance charge transfer and avoid agglom­
eration of active materials in the charge/discharge processes. Based on
the advantages of mixed-metal selenide and RGO, it is worth exploring
to design novel mixed-metal selenide/RGO composite structures as NIBs
(KIBs) anode materials.
Herein, for the first time, we report a simple method to synthesize
Fig. 1. (a) XRD patterns and (b) TGA analysis of ZnSe/RGO, FeSe2/RGO, and (1:1) ZnSe–FeSe2/RGO composites. XPS spectrum of Fig. 1(d) Zn 2p, (e) Fe 2p, (f) Se
3d region for the (1:1) ZnSe–FeSe2/RGO composites.
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Journal of Power Sources 455 (2020) 227937
ZnSe–FeSe2/RGO composites using Fe/Zn-MOF-5 as a template. As a
novel anode material, the ZnSe–FeSe2/RGO composites evidently
display better electrochemical property compared with ZnSe/RGO and
FeSe2/RGO. Moreover, the superior electrochemical performance of
ZnSe–FeSe2/RGO electrode is obtained through optimizing the ratios of
ZnSe and FeSe2 in the composites. The ZnSe–FeSe2/RGO with a ZnSe to
FeSe2 ratio of 1:1 exhibits superior capacity for SIBs (439 mAh g 1 after
100 cycles at 100 mA g 1) and KIBs (362 mAh g 1 after 100 cycles at 50
mA g 1).
2. Experimental
2.1. Preparation of ZnSe–FeSe2/RGO
Scheme 1 shows the schematic synthesis processes of ZnSe–FeSe2/
RGO nanocomposities. Firstly, RGO (Shanghai Carbon Source Huigu)
was supersonically redispersed in 30 ml of a solvent mixture of N,N-
Dimethylformamide (DMF) (Sinopharm Reagent) and ethanol (5:3 in
volume ratio) (Sinopharm Reagent). Then, 0.07 mM H2BDC (Sinopharm
Reagent) was added into the RGO suspensions. After 10 min stirring, Fe
(acac)3 (Sinopharm Reagent) and Zn(NO3)2⋅6H2O (Sinopharm Reagent)
with total molar number at 0.39 mmol were added into the solution and
continuously stirred for another 15 min. The resultant suspension was
J. Yuan et al.
Fig. 2. SEM images of (a) ZnSe/RGO composites, (b) FeSe2/RGO composites, (c) (1:1) ZnSe–FeSe2/RGO composites, EDS mapping of (d) (1:1) ZnSe–FeSe2/RGO
composites, HRTEM image of (e,f) (1:1) ZnSe–FeSe2/RGO composites at different magnifications.
transferred into Teflon-lined autoclave and maintained at 100 � C for 6 h.
The precipitate was collected and washed several times using DMF, and
dried at 80 � C overnight. To get ZnSe–FeSe2/RGO composites, the
Fe–Zn-MOF-5 and Se power with mass ratio of 1:2 were mixed by
grinding. Then, the mixture was put into a ceramic boat. The boat was
covered with Al-foil and selenization was carried out at 350 � C for 2 h in
the Ar atmosphere with 2 � C/min ramping. After selenization, the
temperature of furnace was raised slowly (3 � C/min) to 530 � C, and the
calcination was keeping 3h in the same atmosphere.
2.2. Materials characterizations
The morphologies of products were investigated by scanning elec­
tron microscopy (SEM SU8010, Hitachi) and the microstructure of
products is identified through transmission electron microscopy (TEM
JEM-2010). The crystal structures of products were confirmed by X-ray
diffractometer (XRD DX2700) and Raman spectroscopy (Lab­
RAMHR800). The chemical components of samples were analyzed by X-
ray photoelectron spectroscopy (XPS, Escalab 250xi). The weight ratio
in the products was examined through Thermogravimetric analysis
(TGA,TA-Q600).
2.3. Electrochemical measurements
Electrochemical performances were measured in a 2032-type coin
cell. 70% active material powders, 10% carboxymethyl cellulose (CMC)
(DoDoChem), and 20% conductive carbon black (DoDoChem) were
mixed in water to form slurry through grinding. The slurry was pasted
onto Cu-foil, which was utilized as the working electrode. The argon
filled glove box was used to assemble half cells with sodium foil as the
counter electrode. The solution of 1 M NaClO4 EC/PC (1:1 in volume)
with 10% FEC was adopted as electrolyte (DoDoChem). The galvano­
static charge/discharge was tested using NEWARE battery testers. Cyclic
voltammetry (CV) and electrochemical impedance measurements can be
obtained using Princeton Applied Research Versa STAT 4 workstation.
For K-ion batteries, K metal was utilized as counter electrode and the 1
M potassium hexafluorophosphate (KPF6) in DME was adopted as
electrolyte (DoDoChem).
3. Result and discussion
The XRD patterns of ZnSe/RGO, FeSe2/RGO, ZnSe–FeSe2/RGO
composites with ZnSe to FeSe2 ratio of 1:1 ((1:1) ZnSe–FeSe2/RGO
composites) are displayed in Fig. 1. All the diffraction peaks of ZnSe/
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Journal of Power Sources 455 (2020) 227937
RGO and FeSe2/RGO composites can be well indexed to the standard
diffraction of ZnSe (JCPDS:37–1641) and FeSe2 (JCPDS:12–291)
(Fig. 1a). For ZnSe–FeSe2/RGO composites, all the diffraction peaks are
indexed to both ZnSe and FeSe2 phases, implying the coexistence of ZnSe
and FeSe2. Fig. S1 shows the Raman spectra of (1:1) ZnSe–FeSe2/RGO
composites. Two characteristic modes at around 1351 and 1589 cm 1
can be assigned to D band and G band, respectively. The higher D band
(ID/IG ¼ 1.05) reflects the reduction of GO in the ZnSe–FeSe2/RGO
composites. Fig. 1b presents the thermogravimetric analysis (TGA) of
ZnSe/RGO, FeSe2/RGO, ZnSe–FeSe2/RGO composites. It can be seen
that the weight losses of ZnSe/RGO, FeSe2/RGO, (1:1) ZnSe–FeSe2/RGO
composites are 67%, 80%, and 70%, respectively, in the temperature
range of 50–750 � C. The slight weight increases from 300 to 360 � C for
the three samples correspond to the formation of metal oxide and SeO2.
After 400 � C, there are significant weight decreases for the three prod­
ucts because of the volatilization of SeO2 and oxidation of RGO. Based
on the reaction formula in the inset of Fig. 1b, the mass contents of ZnSe,
FeSe2 and ZnSe–FeSe2 in the ZnSe/RGO, FeSe2/RGO, ZnSe–FeSe2/RGO
composites are calculated to be 59%, 53%, 63%, respectively [35,36].
The surface components and chemical states for the ZnSe/RGO,
FeSe2/RGO, ZnSe–FeSe2/RGO composites are analyzed using XPS. As
shown in the survey spectrum (Fig. 1c) of the ZnSe–FeSe2/RGO com­
posites, all the elements of Zn, Fe, Se, C, and O were observed. In the Zn
2p XPS spectrum for the ZnSe–FeSe2/RGO sample (Fig. 1d), the signals
centered at 1021.7 and 1147.7 eV are belong to Zn 2p3/2 and Zn 2p1/2,
respectively, corresponding to Zn 2p of ZnSe/RGO [37]. In the Fe 2p XPS
spectrum for the ZnSe–FeSe2/RGO sample (Fig. 1e), the signals at 706.9
and 719.9 eV can be ascribed to Fe 2p3/2 and Fe 2p1/2 of FeSe2,
respectively [38]. For the Se 3d XPS spectrum (Fig. 1f), two peaks
centered at 54.6 and 56.1 eV belong to Se 3d5/2 and Se 3d3/2, respec­
tively. Additionally, there is a peak at 58.8 eV corresponding to the SeOx
bond, which may be due to the incomplete reaction [39]. Fig. S2 shows
an XPS spectrum of C1s; The peaks at 284.8, 286.4, and 288.9 eV
correspond to C–C, C–O, and C– – O bands, respectively [40].
The morphologies and microstructures of ZnSe/RGO, FeSe2/RGO,
ZnSe–FeSe2/RGO composites are characterized by SEM and HRTEM. As
shown in Fig. 2a and b, the ZnSe/RGO and FeSe2/RGO composites are
composed of ZnSe nanoparticles with RGO and FeSe2 nanorods with
RGO, respectively. For ZnSe–FeSe2/RGO composites (Fig. 2c), it is can
be seen the composites are combined by ZnSe nanoparticles, FeSe2
nanorods, and RGO. The Energy-dispersive system (EDS) mapping for
the ZnSe–FeSe2/RGO composites testifies that zinc (Zn), iron (Fe), and
selenium (Se) are homogeneously distributed in the ZnSe–FeSe2/RGO
composites (Fig. 2d). The HRTEM of ZnSe–FeSe2/RGO composites
J. Yuan et al.
Fig. 3. Cyclic voltammetry of (a) ZnSe/RGO composites, (b) FeSe2/RGO composites, (c) (1:1) ZnSe–FeSe2/RGO composites at the scan rate of 0.1 mV s 1 in SIBs.
Charge/discharge profiles for (d) ZnSe/RGO composites, (e) FeSe2/RGO composites, (f) (1:1) ZnSe–FeSe2/RGO composites at the current of 100 mA g 1 in SIBs.
(Fig. 2f) shows that interplanar crystal distance of 0.329 nm and 0.258
nm are found, which are attributed to (111) plane of ZnSe and (111)
plane of FeSe2, respectively.
The electrochemical properties of the product for NIB anodes are
investigated by cyclic voltammograms (CV) and galvanostatic cycling.
Fig. 3a, b, and c show the first three CV curves for ZnSe/RGO, FeSe2/
RGO, ZnSe–FeSe2/RGO composites with ZnSe to FeSe2 ratio of 1:1 at a
scan rate of 0.1 mV s 1. For the initial cathodic sweep (Fig. 3a), the
reduction peak located at 0.13 V is associated with the conversion from
ZnSe to Zn/Na2Se, NaZnx, and the growth of the solid electrolyte
interface (SEI) [33]. For the initial anodic sweep, the oxidation peaks at
1.07 V and 1.58 V correspond to the reconstruction of ZnSe. In the
second cathodic sweep, three reduction peaks appear at 0.44 V, 0.62 V
and 1.39 V, respectively. For the third cycle, two reduction peaks appear
at around 0.59 V and 1.39 V, and the total area under reduction and
oxidation peaks shows obvious changes, compared with that of the
second cycle, implying unstable cycling property of the ZnSe/RGO
anode. Furthermore, it indicates that the reduction peaks shift to lower
potentials and the oxidation peaks shift to higher potentials, which
reflect the polarization of the ZnSe/RGO anode [26]. For FeSe2/RGO
electrode, there are three broad reduction peaks at 1.22/0.67/0.39 V
and three oxidation peaks at 1.57/2.05/2.32 V found in the first cycle
(Fig. 3b). The three reduction peaks can be ascribed to the formation of
NaxFeSe2, FeSe, and Na2Se, as well as Fe and Na2Se [35,38]. The three
oxidation peaks can be ascribed to the generation of FeSe and NaxFeSe2
which are transitional products, and FeSe2 which is the ultimate phase.
In the subsequent cycles, the total area under reduction and oxidation
peaks is approximately the same, indicating stable cycling property of
FeSe2/RGO. For ZnSe–FeSe/RGO composites, the first CV curve is
composed of similar reduction and oxidation peaks with ZnSe/RGO and
FeSe2/RGO composites except for a slight in the peak positions (Fig. 3c).
In the subsequent cycles, it is evident that reduction reactions for
ZnSe–FeSe/RGO composites are constituted with the conversion reac­
tion of FeSe2 (reduction peaks at 1.80/1.31/0.49 V, oxidation peaks at
1.50/2.03/2.32 V), and the conversion/alloying reaction of ZnSe
(reduction peaks at 1.31/0.49 V, oxidation peaks at 1.10/1.68 V).
Except for the first cycle, the CV curves of ZnSe–FeSe2/RGO composites
display stable overlap, which indicates reversible and stable cycling
property. It is demonstrated that an irreversible electrochemical reac­
tion for ZnSe/RGO can be restrained by introducing FeSe2 to form
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Journal of Power Sources 455 (2020) 227937
ZnSe–FeSe2/RGO electrode. The electrochemical reactions in the char­
ge/discharge processes are summarized below [35,37,38]:
3.1. Discharge state
ZnSe þ 2Naþ þ2e →Zn þ Na2 Se (1)
XZn þ Naþ þ e →NaZnx (2)
FeSe2 þxNaþ þxe →NaxFeSe2 (3)
FeSe þ 2Naþ þ2e →Fe þ Na2 Se (4)
FeSe þ 2Naþ þ2e →Fe þ Na2 Se (5)
Charge state:
xNa2 Se þ NaZnx →xZnSe þ ð2x þ 1ÞNaþ þ ð2x þ 1Þe (6)
Fe þ 2Na2 Se → Nax FeSe2 þ ð4 xÞNaþ þ ð4 xÞe (7)
Nax FeSe2 → FeSe2 þxNaþ þ xe (8)
Fig. 3d, e and f display the galvanostatic charge-discharge curves for
the 1st, 15th, 30th, 45th, 60th, 75th, 90th of ZnSe/RGO, FeSe2/RGO,
and ZnSe–FeSe2/RGO composites with ZnSe to FeSe2 ratio of 1:1 at 100
mA g 1, respectively. The charge/discharge plateaus of the three sam­
ples are well matched with CV results for the first cycle. In the first cycle,
ZnSe/RGO, FeSe2/RGO, and ZnSe–FeSe2/RGO composites deliver
discharge/charge capacity of 615/453, 523/353, and 648/464 mAh
g 1, respectively, and the coulombic efficiency for the three sample are
74%, 67%, and 72% respectively. The low coulombic efficiency for these
electrodes can be associated with the SEI generation and some irre­
versible reactions, which has been reported for other metal selenide
used as NIBs anodes. ZnSe–FeSe2/RGO composite exhibits a stable
discharge capacity of about 448 mAh g 1 after 15 cycles. In contrast,
ZnSe/RGO composite exhibits a fast discharge capacity fading and
FeSe2/RGO composite exhibits a stable discharge capacity of approxi­
mately 341 mAh g 1 after 15 cycles. It is obvious that the ZnSe–FeSe2/
RGO composite shows a higher reversible capacity compared with ZnSe/
RGO or FeSe2/RGO composite, which should be assgained to the syn­
ergistic effects of ZnSe–FeSe2/RGO composite [26].
J. Yuan et al. Journal of Power Sources 455 (2020) 227937

1
Fig. 4. (a) Capacity retention of ZnSe/RGO composites, FeSe2/RGO composites, and (1:1) ZnSe–FeSe2/RGO composites at 100 mA g in SIBs. (b) Rate capability of
ZnSe/RGO composites, FeSe2/RGO composites, and (1:1) ZnSe–FeSe2/RGO composites in SIBs.

Fig. 5. AC impedance spectra of (a) ZnSe/RGO composites, (b) FeSe2/RGO composites, (c) (1:1) ZnSe–FeSe2/RGO composites after 1, 5, and 50 cycles, respectively
in SIBs. (Inset: equivalent electrical circuit for the fitting).

To confirm the contribution of ZnSe and FeSe2 for the electro­

chemical performance of ZnSe–FeSe2/RGO composite, cycling perfor­
mances of ZnSe–FeSe2/RGO with different ZnSe to FeSe2 ratios are
presented in Fig. 4a. ZnSe/RGO composite exhibits high specific ca­
pacity in the initial several few cycles, but the capacity attenuation is
severe in subsequent cycles. For FeSe2/RGO composite, although the
initial capacity is not as high as that of ZnSe/RGO composite, FeSe2/
RGO electrode shows a reversible capacity of 332 mAh g 1. When
constituting ZnSe–FeSe2/RGO composites with ZnSe to FeSe2 ratios of
7:3, 1:1, 3:7, the first discharge capacity is increased to 748, 647, 763
mAh g 1, and high stable capacities with value of 395, 439, and 365
mAh g 1 after 100 cycles are obtained, respectively. Based on these
electrochemicl results it can be seen that ZnSe–FeSe2/RGO electrode
exhibits better electrochemicl performances than ZnSe/RGO or FeSe2/
RGO electrode, and it is proved that the optimized ratio for the ZnSe to
FeSe2 is 1:1 for getting superior reversible capacity. The superior cycling
performance of the ZnSe–FeSe2/RGO electrode can be comparable to
those of metal selenide based electrode materials in previous reports
(Table S1).
Fig. 4b shows the rate performances of ZnSe/RGO, FeSe2/RGO, and
(1:1) ZnSe–FeSe2/RGO composites in the range of 0.1–10 A g 1. The
discharge capacities for the ZnSe–FeSe2/RGO composite are 407, 374,
364, 339, 290, 237, and 147 mAh g 1 at different current density of 0.1,
0.2, 0.3, 0.5. 1, 2, 5, and 10 A g 1, respectively. Further, As the current Scheme 2. Discharge/charge mechanism of ZnSe–FeSe2/RGO composites
density decreases to 0.1 mA g 1, the specific capacity can recover to 387 anode in a sodium ion battery.
mAh g 1, which reveals the excellent rate performance of the ZnSe–F­
eSe2/RGO composite. It is observed that ZnSe–FeSe2/RGO composite
be seen from Fig. 5b the Nyquist plots for the three electrodes are consist
exhibits better rate performance than ZnSe/RGO composite, which
of solution resistance (Rs), the resistance of the SEI film (Rf), and transfer
demonstrates that introducing FeSe2 to form mixed-metal selenide/RGO
resistance (Rct) [15,41]. The semicircles in the medium-frequency range
is beneficial to get superior rate performance.
are responsible for charge transfer resistance. As shown in Table S2, the
The electrochemical impedance spectra (Fig. 5) was unitized to
Rct values for the three electrodes increased after 50 cycles, implying the
confirm the superior electrochemical property of (1:1) ZnSe–FeSe2/RGO
structure change of electrode during cycling. Compared with ZnSe/RGO
composite compared with ZnSe/RGO and FeSe2/RGO composite. It can
and FeSe2/RGO composite, ZnSe–FeSe2/RGO composite exhibits a

5
J. Yuan et al.
Fig. 6. Cyclic voltammetry of (a) (1:1) ZnSe–FeSe2/RGO composites at the scan rate of 0.1 mV s 1 in KIBs. Charge/discharge profiles for (b) (1:1) ZnSe–FeSe2/RGO
composites at 50 mA g 1 in KIBs, Capacity retention of (c) (1:1) ZnSe–FeSe2/RGO composites 50 mA g 1 in KIBs.
smaller increase of Rf þ Rct with the value from 325 to 345 Ω as the
number of cycles increased from 5 to 50, which indicates that
ZnSe–FeSe2/RGO composite exhibits high structural stability of in the
repeated charge/discharge processes.
On the basis of above electrochemical results, we can concluded that
ZnSe–FeSe2/RGO composite exhibits superior electrochemical proper­
ties for SIBs, which can be associated with its unique composition with
FeSe2 nanorod, ZnSe nanoparticle, and RGO. The FeSe2 and ZnSe have
different reaction potentials, as illustrated in Scheme 2, according to the
CV results (Fig. 3). In the first cathodic process, FeSe2 was first reduced
to form NaxFeSe2. Then, NaxFeSe2 was reduced to form FeSe and Na2Se,
and ZnSe was reduced to form Zn and Na2Se, respectively (discharge 1).
In the continuous discharging process (discharge 2), FeSe was reduced
to form Fe and Na2Se while Zn remained inactive state. At the last step of
the cathodic process (discharge 3), Zn reacts with sodium to form NaZnx
while Fe remained stable state. Therefore, ZnSe and FeSe2 can alter­
nately buffer the stress of Naþ insertion in the cycling process because of
the multistep redox reaction mechanism [23,42]. Additionally, the RGO
act as a conductive network to enhance charge transfer and avoid
agglomeration of ZnSe and FeSe2 in the charge/discharge processes. It is
emphasized that ZnSe has made a primary contribution to the high ca­
pacity of ZnSe–FeSe2/RGO composites because of its high electro­
chemical activity, while FeSe2 can improve with electrochemical
cyclability of the ZnSe–FeSe2/RGO electrode due to its electrochemical
stability.
The superior electrochemical performance of ZnSe–FeSe2/RGO
composites as anodes of NIBs prompts us to extend their potential
application for KIBs anode. Fig. 6a displays the first three CV curves for
(1:1) ZnSe–FeSe2/RGO composites at a scan rate of 0.1 mV s 1. For the
initial cathodic sweep, the peak at 0.13 V can be ascribed to Kþ insertion
reaction, subsequent conversion/alloying reaction, and the formation of
SEI film. For the initial anodic sweep, the broad peaks located at 0.87 V
and 1.70 V can correspond to reconstruction of ZnSe and FeSe2. In the
subsequent cycles, the CV profifiles of ZnSe–FeSe2/RGO composites
show stable overlap, implying reversible and stable cycling perfor­
mance. Fig. 6b shows the charge-discharge profifiles for the 1st, 15th,
30th, 45th, 60th, 75th, 90th cycle of (1:1) ZnSe–FeSe2/RGO composites
at 50 mA g 1. It is observed that the charge/discharge plateaus of
ZnSe–FeSe2/RGO composites are according with the CV result in the
first cycle. In the first cycle, the ZnSe–FeSe2/RGO composites exhibit a
discharge/charge capacity of 527/405 mAh g 1 with a lower coulombic
efficiency of 77%. The coulombic efficiency quickly rises to 98% from
the 15th cycle and stabilizes above 98% in the subsequent cycles. Fig. 6c
presents the cycling ability of ZnSe–FeSe2/RGO composites at 50 mA
g 1. The ZnSe–FeSe2/RGO displays stable discharge capacity of 363
mAh g 1 after 100 cycles. The excellent cycling property of ZnSe–FeSe2/
RGO composites confirms that ZnSe–FeSe2/RGO composites can be used
as effective anode materials for KIBs.
6
Journal of Power Sources 455 (2020) 227937
4. Conclusions
In conclusion, the ZnSe–FeSe2/RGO composites were successfully
fabricated by a facile strategy using Fe/Zn-MOF-5 as a sacrificial tem­
plate. Benefiting from the synergistic effects of the unique architecture
of ZnSe–FeSe2/RGO composites, the ZnSe–FeSe2/RGO electrode ex­
hibits a superior cyclability for SIBs and KIBs anode. The multistep redox
reaction mechanism in ZnSe–FeSe2/RGO composites can buffer the
stress of Naþ insertion in the cycling process. Particularly, as for SIBs, it
is demonstrated that the ZnSe has made a primary contribution to the
high capacity of ZnSe–FeSe2/RGO composites due to its high electro­
chemical activity, while FeSe2 can improve the electrochemical cycla­
bility of the ZnSe–FeSe2/RGO electrode because of its electrochemical
stability. It is expected that this effective strategy can be extended to
constitute other mixed-metal selenide based materials for metal-ion
battery application.
Author statement
I have made substantial contributions to the conception or design of
the work; or the acquisition, analysis, or interpretation of data for the
work; I have drafted the work or revised it critically for important in­
tellectual content; And I have approved the final version to be published;
And I agree to be accountable for all aspects of the work in ensuring that
questions related to the accuracy or integrity of any part of the work are
appropriately investigated and resolved. All persons who have made
substantial contributions to the work reported in the manuscript.
Declaration of competing interest
We declare that we have no financial and personal relationships with
other people or organizations that can inappropriately influence our
work, there is no professional or other personal interest of any nature or
kind in any product, service and/or company that could be construed as
influencing the position presented in, or the review of, the manuscript
entitled.
Acknowledgments
This work was financially supported by Natural Science Foundation
of Jiangxi (20171BAB201014), Foundation of Education Department of
Jiangxi (J60933). Xi’an Science and Technology Project of China
(201805037YD15CG21(20). Open Fund of Jiangsu Key Laboratory of
Electrochemical Energy Storage Technologies (No. EEST2019-1).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jpowsour.2020.227937.
J. Yuan et al. Journal of Power Sources 455 (2020) 227937

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