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Nitrogen-doped carbon sphere encapsulating antimony-cobalt antimony binary nanoseeds as promising anode material for high performance lithium ion battery
Journal Pre-proof Nitrogen-doped carbon sphere encapsulating antimony-cobalt antimony binary nanoseeds as promising anode material for high performance lithium ion battery Zhonghua Zhang, Xiujuan Yan, Chunru Li, He Song, Changming Mao, Hongrui Peng, Guicun Li PII:
S0925-8388(19)34746-2
DOI:
https://doi.org/10.1016/j.jallcom.2019.153500
Reference:
JALCOM 153500
To appear in:
Journal of Alloys and Compounds
Received Date: 18 September 2019 Revised Date:
11 December 2019
Accepted Date: 21 December 2019
Please cite this article as: Z. Zhang, X. Yan, C. Li, H. Song, C. Mao, H. Peng, G. Li, Nitrogen-doped carbon sphere encapsulating antimony-cobalt antimony binary nanoseeds as promising anode material for high performance lithium ion battery, Journal of Alloys and Compounds (2020), doi: https:// doi.org/10.1016/j.jallcom.2019.153500. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier B.V.
Author contributions section Guicun Li: Conceptualization, Methodology. Zhonghua Zhang: Writing-Reviewing and Editing Xiujuan Yan: Writing-Original draft preparation. Chunru Li: Software, Validation. He Song: Data curation. Changming Mao: Visualization, Investigation. Hongrui Peng: Supervision.
Graphic abstract
1
Nitrogen-doped carbon sphere encapsulating antimony-cobalt antimony binary
2
nanoseeds as promising anode material for high performance lithium ion battery
3 4
Zhonghua Zhang, Xiujuan Yan, Chunru Li, He Song, Changming Mao, Hongrui Peng and
5
Guicun Li*
6
College of Materials Science and Engineering, Qingdao University of Science and
7
Technology, Qingdao 266042, China.
8 9
*Corresponding authors E-mail: [email protected].
10 11 12 13 14 15 16 17 18 19 20 21 22 23 1
1
Abstract
2
As a high capacity anode material, antimony and their alloys receive increasing research
3
interest. However, the large volume change during cell cycling still hinders their practical
4
application. Herein, a new type of nitrogen-doped carbon sphere encapsulating antimony-cobalt
5
antimony binary nanoseeds is developed as anode material for Lithium ion batteries by a
6
combined polydopamine coating and annealing method. The incorporation with CoSb2 and
7
nitrogen-doped carbon matrix not only guarantees the high electronic conductivity, but could
8
effectively alleviate the volume changes during cell cycling. The composites consisting of
9
intermetallic CoSb2 electrode for LIBs exhibit the excellent charge/discharge rate capability of
10
320.2 mAh g−1 at 10.0 A g−1 and the high specific capacity of 878.2 mAh g−1 after 500 cycles at 1
11
A g−1, which offers a potential for the material design of the high performance of lithium-ion
12
batteries.
13 14 15
Keywords: Anode; Binary nanoseeds; Intermetallic CoSb2; Lithium-ion batteries
16 17 18 19 20 21 22 2
1
1. Introduction
2
Lithium ion batteries (LIBs) have attracted a wide attention for efficient energy storage and
3
successful applications in portable electronic devices and hybrid electric vehicles [1-3]. However,
4
their commercial applications still require higher performance of LIBs, including high energy
5
density, good rate performance and long lifetime [4]. Thus, unremitting efforts have been devoted
6
to novel alloy-type anode materials (involving Sn, Sb, etc.) with high theoretical capacities for
7
LIBs [5]. Compared with commercial graphite anode (372 mAh g−1), antimony (Sb) as anode
8
candidate has high theoretical capacity of 660 mAh g−1 and holds great promises for high energy
9
LIBs [6]. However, the volume change of ~150% during Li-ion insertion/extraction process leads
10
to rapid capacity decay, which hampers its practical application [7]. Therefore, exploiting the
11
antimony-based nanocomposites with satisfactory performance is highly desired.
12
To further enhance electrochemical performance of antimony-based anode materials, one of
13
effective strategy is to constructing nanocomposites with both antimony and carbonaceous
14
materials. Specifically, carbonaceous materials not only buffer the volume expansion and avoid
15
anode pulverization, but serve as a good conductive material to improve the electron transfer [8].
16
For instance, Lou et al. [9] have synthesized Sb@C coaxial nanotubes through a carbon-coating
17
and thermal-reduction strategy, which deliver a high specific capacity of 310 mAh g−1 at 20 A g−1
18
for sodium-ion batteries. Cao et al. [10] have reported the pitaya-like Sb@C microspheres, which
19
display high sodium-ion storage performances. Zhou et al. [11] have synthesized Sb nanoparticles
20
decorated on N-rich carbon nanosheets via a sol-gel route, exhibiting a reversible capacity of 220
21
mAh g−1 at ultrahigh charge-discharge rate of 2000 mA g−1 after 180 cycles for sodium-ion
22
batteries. 3
1
Designing antimony-based alloy also represents an effective strategy to accommodate the
2
volume changes and thus enhance the cycling stability [12, 13]. Introducing other metal matrix
3
(such as copper, nicke, tin, zincl and so on) to form alloy compounds with antimony could be
4
served
5
intercalation/de-intercalation of lithium ions [14-17]. Different kinds of metal elements and
6
antimony alloy compounds have been designed and prepared to be employed as anode materials
7
for battery applications. By a simple and inexpensive colloidal synthesis, Kovalenko et al. [18]
8
have synthesized SnSb nanoalloys, which maintain a high capacity of ~890 mAh g−1 after 100
9
cycles at a rate of 200 mA g−1. Liu et al. [15] have presented the metal-organic framework-derived
10
NiSb alloy embedded into hollow carbon spheres, exhibiting outstanding rate capability. Madhavi
11
et al. [19] have also reported the melt-spun Fe-Sb intermetallic alloy anode, which show an
12
excellent cycling performance.
as
a
buffer,
which
alleviates
the
volume
expansion
caused
by
the
13
In order to further improve the lithium-ion storage properties of cobalt-antimony alloys,
14
many different strategies have been adopted to prepare different cobalt-antimony alloys. Zhao et al.
15
[20] prepared the CoSb3 particles with nanometer scale by solvothermal route, which exhibit the
16
large reversible capacity and good cycling stability. Lou et al. [13] have obtained CoSb3/C
17
nanoparticles chains via a second growth process. Cheol-Min Park et al. [21] have synthesized the
18
compounds Sb, CoSb/C, CoSb2/C, and CoSb3/C by mechanical ball milling, and the CoSb2/C
19
composites show the best cyclic stability.
20
Herein, a new type of nitrogen-doped carbon sphere encapsulating antimony-cobalt antimony
21
binary nanoseeds (Sb/CoSb2@C) is developed as anode material for LIBs by a combined
22
polydopamine coating and annealing method (Fig. 1). Compared with the previous materials of 4
1
metal antimony and cobalt-antimony alloys, the as-constructed Sb/CoSb2@C nanoparticles not
2
only possess the high capacity ascribed to the integration of metal antimony, but exhibit excellent
3
cycling stability due to the introduction of the CoSb2. In addition, the nanosized structure and
4
carbonaceous surface layer play important roles in improving the rate performance of the samples.
5
Our work demonstrates an integrated design of nitrogen-doped carbon sphere encapsulating
6
antimony-cobalt antimony binary nanoseeds as anode for lithium-ion battery, which may provide
7
some inspiration for functional materials with improved lithium-ion storage performances.
8
2. Experimental section
9
2.1. Synthesis of Sb/CoSb2@C nanocomposites:
10
All chemicals were used without any further purification. 3 mmol NaOH and 2 mmol of
11
tartaric acid were dissolved in 40 mL distilled water under stirring. After the tartaric acid is
12
completely dissolved, 1 mmol SbCl3 was added to the solution and stirred until dissolved. 3 mmol
13
thioacetamide, 0.4 g polyvinylpyrrolidone (PVP) and 0.5 mmol CoCl2 were sequentially added
14
into the above solution and stirred for 30 min. The mixture was transferred to 80 mL Teflon
15
reactor, which was maintained at 150 °C for 12 h. After the hydrothermal treatment, the obtained
16
brown precipitate which was named as CoSb-S Precursor was collected by centrifugal process,
17
and washed with deionized water and ethanol for several times. 0.1 g of the CoSb-S Precursor
18
obtained by drying at 60 °C overnight and 1 mmol Tris(hydroxymethyl)methyl aminomethane
19
were added into 100 mL distilled water. After being ultrasonic treatment for 30 min, 0.1 g
20
dopamine hydrochloride was added to the suspension and stirred at room temperature for 12 h.
21
After centrifugation, washing and drying, the black sample which was named CoSb-S
22
Precursor@PDA was gained. Finally, the Sb/CoSb2@C nanocomposite was obtained by annealing 5
1
in Ar flow at 500 °C for 2 h with a temperature ramp of 3 °C min−1. Similarly, Sb@C sample were
2
prepared by a similar method, except for adding 2 mmol thioacetamide and 0.4 g
3
polyvinylpyrrolidone before the hydrothermal treatment. Sb/CoSb2 sample were prepared by a
4
similar method, except for annealing the obtained CoSb-S Precursor directly after centrifugal and
5
washing process.
6
2.2. Materials characterizations
7
The composites and phase of materials were characterized by X-ray diffraction analysis
8
(XRD, Rigaku diffractometer, Cu Kα, λ=1.54178 Å). X-ray photoelectron spectroscopy (XPS) was
9
conducted on a Thermo X-ray photoelectron Spectrometer (ESCALAB 250XI) with Al Kα
10
(hv=1486.6 eV) X-ray source. Thermogravimetric analysis (TGA) was used to determine the Sb
11
and Co content in the sample by using the instrument (NETZSCH STA 449C, Germany) from
12
room temperature to 800 °C with a heating rate of 10 °C min−1. The surface morphology and
13
elemental distribution of materials were characterized by scanning electron microscopy (SEM,
14
JSM-6700F, JEOL) and energy dispersive spectroscopy (EDS, JSM-6700F, JEOL) respectively.
15
The transmission electron microscope (TEM, JEM-2100, JEOL) was also used to investigate the
16
microstructure of nanocomposites. The Brunauer-Emmett-Teller (BET) surface area and pore
17
distribution were determined with the surface area and porosimetry system (Micromeritics, ASAP
18
2020).
19
2.3. Electrochemical measurements:
20
The working electrodes containing the active samples, carbon black super-P and poly(vinyl
21
difluoride) with weight ratio of 7: 2: 1 were prepared on Cu foil. After dried in a vacuum oven at
22
120 °C for 12 h, the obtained electrodes were punched into circular slices with a diameter of 12 6
1
mm. CR2032-type coin cells were assembled with working electrodes, counter electrode (Pure
2
lithium), separator (Celgard 2500 membrane) and Li-ion electrolyte (1 M LiPF6 dissolved in
3
ethylene carbonate/dimethyl carbonate with 1:1 vol %) in Ar-filled glove box. Cyclic voltammetry
4
(CV) at scanning rate of 0.1 mV s−1 in the potential range of 0.01-3.0 V and electrochemical
5
impedance spectroscopy (EIS) at frequency range from 100 kHz to 10 MHz with an amplitude of
6
10.0 mV were measured on Metrohm (PGSTAT302N) Autolab electrochemical workstation.
7
Cycling performances were recorded on Land cell test station (CT2001A) in the voltage range of
8
0.01-3.0 V (vs. Li+/Li).
9
3. Results and discussion
10
X-ray diffraction (XRD) patterns of the Sb/CoSb2@C and Sb@C sample are presented in Fig.
11
2. It is noted that most of the diffraction peaks of the Sb/CoSb2@C sample can be ascribed to the
12
hexagonal structure of metallic Sb (JCPDS: 35-0732), and the identified peaks at 28.7°, 40.1° and
13
41.9° correspond to the (012), (104) and (110) plane of Sb, respectively (Fig. 2a). In addition,
14
three diffraction main peaks centered at 30°-35° (Fig. 2b) correspond to (-121), (210) and (200)
15
plane of monoclinic CoSb2 (JCPDS: 29-0126). These analysis results indicate that the
16
Sb/CoSb2@C sample mainly consists of Sb, CoSb2. The XRD pattern of the Sb@C sample shows
17
that all the diffraction peaks correspond to hexagonal structure of metallic Sb (JCPDS: 35-0732),
18
and there are no obvious diffraction peaks at 30°-35°, which is different from the XRD pattern of
19
Sb/CoSb2@C sample (Fig. 2c).
20
To gain further information on the the surface elemental compositions of the Sb/CoSb2@C
21
sample, the X-ray photoelectron spectroscopy (XPS) are investigated. The survey spectra confirm
22
the presence of Sb, Co, C, N and O in the Sb/CoSb2@C sample (Fig. S1). The high-resolution 7
1
spectra of these elements are investigated to analyze their chemical states, and the results is shown
2
in Fig. 3a–d. Fig. 3a shows the peaks for Sb 3d5/2, Sb 3d3/2 and O 1s. The peaks at 528.9 and 538.6
3
eV could be attributed to Sb 3d5/2 and Sb 3d3/2 from metallic Sb and CoSb2 [22]. The peaks at 530.
4
9 and 540.2 eV can be ascribed to Sb 3d5/2 and Sb 3d3/2 from SbOx, respectively [22]. The peaks at
5
532.1 eV can be ascribed to O 1s from H2O, CO2 and SbOx, which may be related to the contact
6
between the surface of the sample and the air [22, 23]. The XPS spectra of pure metal antimony
7
and CoSb2 have also been investigated (Fig. S2 and Fig. S3a). Compared to pure metal Sb (529.9
8
and 539.1 eV for metallic Sb) and CoSb2 (527.4 and 536.8 eV for metallic Sb), it is noted that the
9
characteristic peaks of metallic Sb for Sb/CoSb2@C shift to the lower and higher binding energy
10
with the opposite direction. This result indicates a decreased electron cloud density around CoSb2
11
and an increased cloud density around metal Sb. The electron transfer from CoSb2 to metal Sb
12
might confirm the enhanced interaction and strong coupling between CoSb2 and Sb, arising from
13
the enhanced interaction between valence-band potentials and Pauling electronegativity of Sb–Co
14
covalency [24, 25]. Meanwhile, the Co 2p3/2 and Co 2p1/2 spectrum of Sb/CoSb2@C and CoSb2
15
are shown in Fig. 3b and Fig. S3b, respectively. As for the Co 2P XPS spectrum of Sb/CoSb2@C,
16
two peaks at 781.0 and 796.5 eV can be ascribed to Co 2p3/2 and Co 2p1/2 from metallic Co of
17
CoSb2 [26]. Two peaks at 786.3 and 797.7 eV are characteristics of Co 2p3/2 and Co 2p1/2 from
18
CoOx, which is the product of the oxidation of cobalt on the surface of the sample by air [26, 27].
19
Two shake-up satellites appear at 786.3 and 802.2 eV [26]. Compared to CoSb2 (777.9 and 792.7
20
eV for metallic Co), it is observed that the characteristic peaks of metallic Co for Sb/CoSb2@C
21
shift to a higher binding energy, indicating a decreased electron cloud density around CoSb2. The
22
electron cloud bias from CoSb2 to Sb is solid evidence of enhanced interaction and strong 8
1
coupling between CoSb2 and Sb. Fig. 3c shows the high-resolution spectra of C 1s, which consist
2
of three main peaks at 284.8, 285.5 and 287.4 eV corresponding to the C–C, C–N, C–O species,
3
respectively [28]. The C 1s spectra of N-doped carbon derived from annealed polydopamine
4
shown in Fig. S4 exhibited three peaks at 284.8, 285.8 and 287.9 eV, which were similar with the
5
C 1s spectra of Sb/CoSb2@C. The N 1s spectra (Fig. 3d) exhibit two peaks at 398.6 and 400.3 eV,
6
which can be assigned to pyridinic N and pyrrolic N, respectively [28-30]. In addition, the carbon,
7
nitrogen, antimony and cobalt content on the surface of the sample measured by XPS was 92.6,
8
5.5, 1.4 and 0.5 atom%, respectively. The signals of carbon, nitrogen, antimony and cobalt on the
9
surface of the Sb/CoSb2@C sample can also be clearly identified in the energy dispersive
10
spectrum (Fig. S5), confirming their existence in Sb/CoSb2@C sample. The analyses of XRD,
11
XPS and EDS suggest that metallic Sb, CoSb2 and nitrogen doped carbon exist in the
12
as-constructed sample.
13
To determine the accurate component contents in the Sb/CoSb2@C sample, TGA was
14
conducted in nitrogen and the air (Fig. S6). The weight loss (27.8%) of the Sb/CoSb2@C sample
15
measured by thermogravimetric test in nitrogen mainly comes from the heat evaporation of
16
metallic antimony due to its lower melting point (630 °C) [31]. After deducting the weight loss of
17
the heat evaporation of metallic antimony, TGA curve of the Sb/CoSb2@C sample in the air
18
unravels that the weight contents of C, Sb and Co in Sb/CoSb2@C sample are about 40.7-41.7%,
19
48.1-59.3% and 0-10.2 wt%, respectively [31-33].
20
The SEM images (Fig. 4a-b) reveal that both the CoSb-S precursor and the Sb/CoSb2@C
21
sample show particle morphology, and the precursors exhibit larger diameters. EDS elemental
22
mapping results (Fig. S7) show the distribution of Sb, C, Co, and N in the Sb/CoSb2@C sample. 9
1
To further reveal the microstructure, TEM images are displayed in Fig.4c-d. As shown in Fig. 4c,
2
the Sb and CoSb2 nanoparticles are embedded into the N-doped carbon nanoparticles, which show
3
amorphous structures (Fig. 4d). The lattices of the Sb and CoSb2 are observed in Fig. 4e-f, in
4
which the marked d-spacing of 0.175 nm and 0.254 nm correspond well to the (202) plane of Sb
5
and the (-212) plane of CoSb2, respectively. The SEM images (Fig. S8a-b) reveal that both the
6
CoSb-S precursor and the Sb@C sample show nanosphere-like morphology with the uniform size,
7
and the precursors also display larger diameters. The BET surface areas of the Sb@C sample and
8
the Sb/CoSb2@C sample are 10.2 and 12.0 m2 g-1 according to the adsorption-desorption data (Fig.
9
S9a), respectively. And the more micropores and mesopores in the Sb/CoSb2@C sample was
10
shown in Fig. S9b.
11
The electrochemical performances of the Sb/CoSb2@C electrode, Sb@C electrode and
12
Sb/CoSb2 electrode for LIBs are measured by CV and galvanostatic charge/discharge tests. In the
13
CV curves of Sb/CoSb2@C electrode (Fig. 5a), the cathodic scan of the first cycle displays that
14
two cathodic peaks at ~0.7 and 0.8 V are attributed to alloying processes of Sb from metallic Sb
15
and CoSb2 with Li, which contains the two phase transitions of Sb into Li2Sb and Li2Sb into Li3Sb
16
[34, 35]. And the weak peak at ~0.4 V demonstrates the formation of solid electrolyte interphase
17
film [36]. The cathodic peak at 1.2 V corresponds to the delithiation reactions of Li3Sb [35]. In the
18
next four cycles, the peaks are basically overlapped, indicating good reversibility of these
19
reactions of Sb/CoSb2@C electrodes. The CV curves of Sb@C electrode (Fig. 5b) show the
20
similar trends except for the different cathodic peak at 1.3 V in the first cycle, which may be
21
attributed to the decomposition of SbOx [37-39]. The CV curves of CoSb2 electrode (Fig. S10)
22
exhibited one cathodic peak at ~0.8 V, and the sharp peak at ~0.3 V arises from the formation of 10
1
solid electrolyte interphase film. In the next four cycles, there are lower intensity of both cathodic
2
and anodic peaks, reflecting that the conversion reaction is not completely reversible, which may
3
be leads to irreversible capacity loss and lower coulombic efficiency. In addition, the curves of
4
Sb@C and Sb/CoSb2 electrodes in the next cycles show imperfect overlaps, indicating the inferior
5
reversibility of Sb@C and Sb/CoSb2 electrodes. The initial three charge and discharge curves of
6
these two composites are shown in Fig. S11a-b. There are the voltage plateaus in these curves,
7
which correspond well to the results of the CV analysis.
8
Fig. 5c and Fig S12 shows the electrochemical performances of Sb@C and Sb/CoSb2@C
9
electrodes at the current densities from 0.1 A g−1 to 5 A g−1, respectively. The electrode capacity
10
was stable at about 958.7 mAh g−1 at 0.1 A g−1, which is close to its theoretical capacity. Even at
11
the high current density of 5 A g−1, the Sb/CoSb2@C electrodes still keep the discharge platform
12
well, which conformed that the present of CoSb2 can efficiency enhance ion/electron transmission.
13
Fig. 5d and Fig. S13 show the rate capability of the Sb/CoSb2@C electrode, the Sb@C electrode
14
and the Sb/CoSb2 electrode at current densities from 0.1 to 10 A g−1. At increasing current
15
densities of 0.1, 0.2, 0.5, 1, 2, 5, 8 and 10 A g−1, the Sb/CoSb2@C electrode delivers the average
16
discharge capacities of 958.7, 864.2, 797.9, 730.4, 647.0, 485.4, 368.8 and 320.2 mAh g−1,
17
respectively. The Sb@C electrode delivers inferior average specific capacities of 889.9, 691.8,
18
572.5, 482.5, 77.2, 36.0 and 31.7 mA h g−1 at 0.1, 0.2, 0.5, 1, 2, 5, 8 and 10 A g−1, respectively,
19
The capacity of Sb/CoSb2@C electrode maintains at a high value when the current density returns
20
to 0.1 A g−1, indicating the good rate capability of Sb/CoSb2@C. Compared to Sb/CoSb2@C
21
electrode, the discharge capacity based on Sb/CoSb2 electrode (Fig. S13) decreases rapidly at
22
current densities of 0.1, 0.2, 0.5, and 1 A g−1, it is noted that the capacity is around 20 mA h g−1 at 11
1
5, 8, and 10 A g−1, this result indicated high stability of Sb/CoSb2@C electrode by polydopamine
2
coating [40]. Consistent conclusion can be reached by the cycling performances. As displayed in
3
Fig. 5e, the Sb/CoSb2@C electrode and the Sb@C electrode exhibit that the charge capacities
4
were maintained at 878.2 and 656.9 mAh g−1 after 500 cycles, respectively. Specially, the
5
Sb/CoSb2@C electrode and the Sb@C electrode retain high coulombic efficiencies of 99.6% and
6
99.1% over 500 cycles, respectively. The Sb/CoSb2 electrode (Fig. S14) delivers an initial specific
7
capacity of ∼825 mA h g−1 but it can maintain a capacity of 99 mA h g−1 after 350 cycles. The
8
electrochemical property of the Sb/CoSb2 electrode seems to be much inferior to that of the
9
Sb/CoSb2@C electrode. It is worth noting that the capacity decays rapidly during the initial 100
10
cycles for the Sb/CoSb2 electrode, which might be ascribed to the formation of unstable SEI film
11
during the repeated lithium ion insertion/extraction due to the lack of conductive carbon outer
12
layer [40]. These electrochemical performance results illustrate the outstanding specific capacity
13
and high cycle stability of the Sb/CoSb2@C electrode. The electrochemical impedance
14
spectroscopy (EIS) measurements of the Sb/CoSb2@C, Sb@C and Sb/CoSb2 electrode before and
15
after cycling were analyzed and shown in Fig. S15a-b. The Sb/CoSb2@C and Sb@C composite
16
electrode exhibit a lower interface impedance than that of the Sb/CoSb2 electrode, indicating
17
improved interfacial properties by introduced carbon out layer, leading to faster charge transfer
18
across the electrode/electrolyte interface. [40] In addition, the linear slope of the Sb@CoSb2@C
19
composite electrode in the low frequency region is higher than that of the Sb@C electrode,
20
suggesting superior Li-ion diffusion of Sb/CoSb2@C. Apart from that, the Sb@CoSb2@C
21
composite electrode exhibits a lower ohmic resistance shown in the enlarged part of Fig. S15a,
22
indicating the higher electronic conductivity of Sb@CoSb2@C composite. As shown in Fig. S15b, 12
1
the electrode resistance of all electrodes are increased after cycling, which are mainly attributed to
2
the formation of SEI film. The Sb/CoSb2@C composite electrode show the highest linear slope
3
compared to the other electrodes, indicating the better electrode kinetics and electrochemical
4
properties of the Sb/CoSb2@C electrode.
5
To further understand the better cycle stability for the Sb/CoSb2@C anode, the morphologies
6
of Sb/CoSb2@C and Sb/CoSb2 after 100 cycles at 1 A g-1 were studied. As shown in Fig. S16a, the
7
structure of the lithiated Sb/CoSb2 electrode was seriously destructed, which changed to irregular
8
chunky particles aggregated by isolated nanoparticles. However, the spherical nanostructure of
9
Sb/CoSb2@C was largely maintained, indicating the relatively higher structural stability to a great
10
extent due to the effective strain/stress accommodation of the resilient carbon layer.
11
Conclusions
12
In conclusion, a new type of nitrogen-doped carbon sphere encapsulating antimony-cobalt
13
antimony binary nanoseeds has been synthesized by annealing the nanospheres containing
14
antimony and cobalt, and Sb/CoSb2@C composites could be employed as a novel composite
15
anode material for LIBs with outstanding specific capacity and extremely high cycle stability.
16
Compared with Sb@C electrode (31.7 mA h g−1) and Sb/CoSb2 electrode (20 mA h g−1), the
17
as-synthesized Sb/CoSb2@C electrode exhibit the excellent charge/discharge rate capability of
18
320.2 mAh g−1 at 10.0 A g−1. More remarkably, the high specific capacity of 878.2 mAh g−1 for
19
LIBs with Sb/CoSb2@C electrode can be well-maintained after 500 cycles at 1 A g−1. The
20
excellent Li-ion storage properties can be attributed to the incorporation with CoSb2 and
21
nitrogen-doped carbon matrix, which not only guarantees the high electronic conductivity, but
22
could effectively alleviate the volume changes during cell cycling. Our work demonstrates an 13
1
integrated design of antimony/cobalt-antimony/N-doped carbon composites, which may provide
2
some inspiration for functional materials with improved lithium-ion storage performances.
3
Acknowledgement
4
This work was supported by the National Natural Science Foundation of China (No.
5
51672146, 21805157, 51972187), the Natural Science Foundation of Shandong Province
6
(ZR2018BEM011, ZR2019MEM043 and ZR2019MB037), the Key R & D project of Shandong
7
Province (2019GGX103034) and the Development Program in Science and Technology of
8
Qingdao (19-6-2-12-cg).
9
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Figure captions
19
Fig. 1 Schematic illustration of the preparation of the Sb/CoSb2@C sample.
20
Fig. 2 XRD patterns of the Sb/CoSb2@C sample (a, b) and the Sb@C sample (c).
21
Fig. 3 High-resolution XPS of the Sb 3d (a), Co 2p (b), C 1s (c) and N 1s (d) in the Sb/CoSb2@C
22
sample. 19
1
Fig. 4 The SEM images of CoSb-S precursor (a), Sb/CoSb2@C sample (b). TEM image of
2
Sb/CoSb2@C sample (c-d). HRTEM lattice image of Sb@C and Sb/CoSb2@C sample (e-f).
3
Fig. 5 The CV curves of the Sb/CoSb2@C electrode (a) and the Sb@C (b) electrode for LIBs at
4
the initial five cycles. (c) The charge/discharge profiles from 0.1 to 5 A g−1 of the Sb/CoSb2@C
5
electrode. The rate performances of the Sb/CoSb2@C electrode and the Sb@C electrode at various
6
current density (d). The cycling performances of the Sb/CoSb2@C electrode and the Sb@C
7
electrode at current density of 1 A g−1 (e).
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 20
1 2 3
Figure 1
4 5
6 7 8 9
Figure 2
10 11
12 21
1 2 3
Figure 3
4
5 6 7 8 9 10 11 12 22
1 2 3 4
Figure 4
5 6
7 8 9 10 11 12 13 14 15 16 23
1 2 3
Figure 5
4
5
24
Highlights The Sb/CoSb2@C is designed combine polydopamine coating and annealing method CoSb2 and nitrogen-doped carbon matrix guarantees the high electronic conductivity The Sb/CoSb2@C composite exhibit the excellent charge/discharge rate capability Sb/CoSb2@C composite could be a promising anode for advanced lithium-ion batteries
Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
S0925-8388(19)34746-2
DOI:
https://doi.org/10.1016/j.jallcom.2019.153500
Reference:
JALCOM 153500
To appear in:
Journal of Alloys and Compounds
Received Date: 18 September 2019 Revised Date:
11 December 2019
Accepted Date: 21 December 2019
Please cite this article as: Z. Zhang, X. Yan, C. Li, H. Song, C. Mao, H. Peng, G. Li, Nitrogen-doped carbon sphere encapsulating antimony-cobalt antimony binary nanoseeds as promising anode material for high performance lithium ion battery, Journal of Alloys and Compounds (2020), doi: https:// doi.org/10.1016/j.jallcom.2019.153500. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier B.V.
Author contributions section Guicun Li: Conceptualization, Methodology. Zhonghua Zhang: Writing-Reviewing and Editing Xiujuan Yan: Writing-Original draft preparation. Chunru Li: Software, Validation. He Song: Data curation. Changming Mao: Visualization, Investigation. Hongrui Peng: Supervision.
Graphic abstract
1
Nitrogen-doped carbon sphere encapsulating antimony-cobalt antimony binary
2
nanoseeds as promising anode material for high performance lithium ion battery
3 4
Zhonghua Zhang, Xiujuan Yan, Chunru Li, He Song, Changming Mao, Hongrui Peng and
5
Guicun Li*
6
College of Materials Science and Engineering, Qingdao University of Science and
7
Technology, Qingdao 266042, China.
8 9
*Corresponding authors E-mail: [email protected].
10 11 12 13 14 15 16 17 18 19 20 21 22 23 1
1
Abstract
2
As a high capacity anode material, antimony and their alloys receive increasing research
3
interest. However, the large volume change during cell cycling still hinders their practical
4
application. Herein, a new type of nitrogen-doped carbon sphere encapsulating antimony-cobalt
5
antimony binary nanoseeds is developed as anode material for Lithium ion batteries by a
6
combined polydopamine coating and annealing method. The incorporation with CoSb2 and
7
nitrogen-doped carbon matrix not only guarantees the high electronic conductivity, but could
8
effectively alleviate the volume changes during cell cycling. The composites consisting of
9
intermetallic CoSb2 electrode for LIBs exhibit the excellent charge/discharge rate capability of
10
320.2 mAh g−1 at 10.0 A g−1 and the high specific capacity of 878.2 mAh g−1 after 500 cycles at 1
11
A g−1, which offers a potential for the material design of the high performance of lithium-ion
12
batteries.
13 14 15
Keywords: Anode; Binary nanoseeds; Intermetallic CoSb2; Lithium-ion batteries
16 17 18 19 20 21 22 2
1
1. Introduction
2
Lithium ion batteries (LIBs) have attracted a wide attention for efficient energy storage and
3
successful applications in portable electronic devices and hybrid electric vehicles [1-3]. However,
4
their commercial applications still require higher performance of LIBs, including high energy
5
density, good rate performance and long lifetime [4]. Thus, unremitting efforts have been devoted
6
to novel alloy-type anode materials (involving Sn, Sb, etc.) with high theoretical capacities for
7
LIBs [5]. Compared with commercial graphite anode (372 mAh g−1), antimony (Sb) as anode
8
candidate has high theoretical capacity of 660 mAh g−1 and holds great promises for high energy
9
LIBs [6]. However, the volume change of ~150% during Li-ion insertion/extraction process leads
10
to rapid capacity decay, which hampers its practical application [7]. Therefore, exploiting the
11
antimony-based nanocomposites with satisfactory performance is highly desired.
12
To further enhance electrochemical performance of antimony-based anode materials, one of
13
effective strategy is to constructing nanocomposites with both antimony and carbonaceous
14
materials. Specifically, carbonaceous materials not only buffer the volume expansion and avoid
15
anode pulverization, but serve as a good conductive material to improve the electron transfer [8].
16
For instance, Lou et al. [9] have synthesized Sb@C coaxial nanotubes through a carbon-coating
17
and thermal-reduction strategy, which deliver a high specific capacity of 310 mAh g−1 at 20 A g−1
18
for sodium-ion batteries. Cao et al. [10] have reported the pitaya-like Sb@C microspheres, which
19
display high sodium-ion storage performances. Zhou et al. [11] have synthesized Sb nanoparticles
20
decorated on N-rich carbon nanosheets via a sol-gel route, exhibiting a reversible capacity of 220
21
mAh g−1 at ultrahigh charge-discharge rate of 2000 mA g−1 after 180 cycles for sodium-ion
22
batteries. 3
1
Designing antimony-based alloy also represents an effective strategy to accommodate the
2
volume changes and thus enhance the cycling stability [12, 13]. Introducing other metal matrix
3
(such as copper, nicke, tin, zincl and so on) to form alloy compounds with antimony could be
4
served
5
intercalation/de-intercalation of lithium ions [14-17]. Different kinds of metal elements and
6
antimony alloy compounds have been designed and prepared to be employed as anode materials
7
for battery applications. By a simple and inexpensive colloidal synthesis, Kovalenko et al. [18]
8
have synthesized SnSb nanoalloys, which maintain a high capacity of ~890 mAh g−1 after 100
9
cycles at a rate of 200 mA g−1. Liu et al. [15] have presented the metal-organic framework-derived
10
NiSb alloy embedded into hollow carbon spheres, exhibiting outstanding rate capability. Madhavi
11
et al. [19] have also reported the melt-spun Fe-Sb intermetallic alloy anode, which show an
12
excellent cycling performance.
as
a
buffer,
which
alleviates
the
volume
expansion
caused
by
the
13
In order to further improve the lithium-ion storage properties of cobalt-antimony alloys,
14
many different strategies have been adopted to prepare different cobalt-antimony alloys. Zhao et al.
15
[20] prepared the CoSb3 particles with nanometer scale by solvothermal route, which exhibit the
16
large reversible capacity and good cycling stability. Lou et al. [13] have obtained CoSb3/C
17
nanoparticles chains via a second growth process. Cheol-Min Park et al. [21] have synthesized the
18
compounds Sb, CoSb/C, CoSb2/C, and CoSb3/C by mechanical ball milling, and the CoSb2/C
19
composites show the best cyclic stability.
20
Herein, a new type of nitrogen-doped carbon sphere encapsulating antimony-cobalt antimony
21
binary nanoseeds (Sb/CoSb2@C) is developed as anode material for LIBs by a combined
22
polydopamine coating and annealing method (Fig. 1). Compared with the previous materials of 4
1
metal antimony and cobalt-antimony alloys, the as-constructed Sb/CoSb2@C nanoparticles not
2
only possess the high capacity ascribed to the integration of metal antimony, but exhibit excellent
3
cycling stability due to the introduction of the CoSb2. In addition, the nanosized structure and
4
carbonaceous surface layer play important roles in improving the rate performance of the samples.
5
Our work demonstrates an integrated design of nitrogen-doped carbon sphere encapsulating
6
antimony-cobalt antimony binary nanoseeds as anode for lithium-ion battery, which may provide
7
some inspiration for functional materials with improved lithium-ion storage performances.
8
2. Experimental section
9
2.1. Synthesis of Sb/CoSb2@C nanocomposites:
10
All chemicals were used without any further purification. 3 mmol NaOH and 2 mmol of
11
tartaric acid were dissolved in 40 mL distilled water under stirring. After the tartaric acid is
12
completely dissolved, 1 mmol SbCl3 was added to the solution and stirred until dissolved. 3 mmol
13
thioacetamide, 0.4 g polyvinylpyrrolidone (PVP) and 0.5 mmol CoCl2 were sequentially added
14
into the above solution and stirred for 30 min. The mixture was transferred to 80 mL Teflon
15
reactor, which was maintained at 150 °C for 12 h. After the hydrothermal treatment, the obtained
16
brown precipitate which was named as CoSb-S Precursor was collected by centrifugal process,
17
and washed with deionized water and ethanol for several times. 0.1 g of the CoSb-S Precursor
18
obtained by drying at 60 °C overnight and 1 mmol Tris(hydroxymethyl)methyl aminomethane
19
were added into 100 mL distilled water. After being ultrasonic treatment for 30 min, 0.1 g
20
dopamine hydrochloride was added to the suspension and stirred at room temperature for 12 h.
21
After centrifugation, washing and drying, the black sample which was named CoSb-S
22
Precursor@PDA was gained. Finally, the Sb/CoSb2@C nanocomposite was obtained by annealing 5
1
in Ar flow at 500 °C for 2 h with a temperature ramp of 3 °C min−1. Similarly, Sb@C sample were
2
prepared by a similar method, except for adding 2 mmol thioacetamide and 0.4 g
3
polyvinylpyrrolidone before the hydrothermal treatment. Sb/CoSb2 sample were prepared by a
4
similar method, except for annealing the obtained CoSb-S Precursor directly after centrifugal and
5
washing process.
6
2.2. Materials characterizations
7
The composites and phase of materials were characterized by X-ray diffraction analysis
8
(XRD, Rigaku diffractometer, Cu Kα, λ=1.54178 Å). X-ray photoelectron spectroscopy (XPS) was
9
conducted on a Thermo X-ray photoelectron Spectrometer (ESCALAB 250XI) with Al Kα
10
(hv=1486.6 eV) X-ray source. Thermogravimetric analysis (TGA) was used to determine the Sb
11
and Co content in the sample by using the instrument (NETZSCH STA 449C, Germany) from
12
room temperature to 800 °C with a heating rate of 10 °C min−1. The surface morphology and
13
elemental distribution of materials were characterized by scanning electron microscopy (SEM,
14
JSM-6700F, JEOL) and energy dispersive spectroscopy (EDS, JSM-6700F, JEOL) respectively.
15
The transmission electron microscope (TEM, JEM-2100, JEOL) was also used to investigate the
16
microstructure of nanocomposites. The Brunauer-Emmett-Teller (BET) surface area and pore
17
distribution were determined with the surface area and porosimetry system (Micromeritics, ASAP
18
2020).
19
2.3. Electrochemical measurements:
20
The working electrodes containing the active samples, carbon black super-P and poly(vinyl
21
difluoride) with weight ratio of 7: 2: 1 were prepared on Cu foil. After dried in a vacuum oven at
22
120 °C for 12 h, the obtained electrodes were punched into circular slices with a diameter of 12 6
1
mm. CR2032-type coin cells were assembled with working electrodes, counter electrode (Pure
2
lithium), separator (Celgard 2500 membrane) and Li-ion electrolyte (1 M LiPF6 dissolved in
3
ethylene carbonate/dimethyl carbonate with 1:1 vol %) in Ar-filled glove box. Cyclic voltammetry
4
(CV) at scanning rate of 0.1 mV s−1 in the potential range of 0.01-3.0 V and electrochemical
5
impedance spectroscopy (EIS) at frequency range from 100 kHz to 10 MHz with an amplitude of
6
10.0 mV were measured on Metrohm (PGSTAT302N) Autolab electrochemical workstation.
7
Cycling performances were recorded on Land cell test station (CT2001A) in the voltage range of
8
0.01-3.0 V (vs. Li+/Li).
9
3. Results and discussion
10
X-ray diffraction (XRD) patterns of the Sb/CoSb2@C and Sb@C sample are presented in Fig.
11
2. It is noted that most of the diffraction peaks of the Sb/CoSb2@C sample can be ascribed to the
12
hexagonal structure of metallic Sb (JCPDS: 35-0732), and the identified peaks at 28.7°, 40.1° and
13
41.9° correspond to the (012), (104) and (110) plane of Sb, respectively (Fig. 2a). In addition,
14
three diffraction main peaks centered at 30°-35° (Fig. 2b) correspond to (-121), (210) and (200)
15
plane of monoclinic CoSb2 (JCPDS: 29-0126). These analysis results indicate that the
16
Sb/CoSb2@C sample mainly consists of Sb, CoSb2. The XRD pattern of the Sb@C sample shows
17
that all the diffraction peaks correspond to hexagonal structure of metallic Sb (JCPDS: 35-0732),
18
and there are no obvious diffraction peaks at 30°-35°, which is different from the XRD pattern of
19
Sb/CoSb2@C sample (Fig. 2c).
20
To gain further information on the the surface elemental compositions of the Sb/CoSb2@C
21
sample, the X-ray photoelectron spectroscopy (XPS) are investigated. The survey spectra confirm
22
the presence of Sb, Co, C, N and O in the Sb/CoSb2@C sample (Fig. S1). The high-resolution 7
1
spectra of these elements are investigated to analyze their chemical states, and the results is shown
2
in Fig. 3a–d. Fig. 3a shows the peaks for Sb 3d5/2, Sb 3d3/2 and O 1s. The peaks at 528.9 and 538.6
3
eV could be attributed to Sb 3d5/2 and Sb 3d3/2 from metallic Sb and CoSb2 [22]. The peaks at 530.
4
9 and 540.2 eV can be ascribed to Sb 3d5/2 and Sb 3d3/2 from SbOx, respectively [22]. The peaks at
5
532.1 eV can be ascribed to O 1s from H2O, CO2 and SbOx, which may be related to the contact
6
between the surface of the sample and the air [22, 23]. The XPS spectra of pure metal antimony
7
and CoSb2 have also been investigated (Fig. S2 and Fig. S3a). Compared to pure metal Sb (529.9
8
and 539.1 eV for metallic Sb) and CoSb2 (527.4 and 536.8 eV for metallic Sb), it is noted that the
9
characteristic peaks of metallic Sb for Sb/CoSb2@C shift to the lower and higher binding energy
10
with the opposite direction. This result indicates a decreased electron cloud density around CoSb2
11
and an increased cloud density around metal Sb. The electron transfer from CoSb2 to metal Sb
12
might confirm the enhanced interaction and strong coupling between CoSb2 and Sb, arising from
13
the enhanced interaction between valence-band potentials and Pauling electronegativity of Sb–Co
14
covalency [24, 25]. Meanwhile, the Co 2p3/2 and Co 2p1/2 spectrum of Sb/CoSb2@C and CoSb2
15
are shown in Fig. 3b and Fig. S3b, respectively. As for the Co 2P XPS spectrum of Sb/CoSb2@C,
16
two peaks at 781.0 and 796.5 eV can be ascribed to Co 2p3/2 and Co 2p1/2 from metallic Co of
17
CoSb2 [26]. Two peaks at 786.3 and 797.7 eV are characteristics of Co 2p3/2 and Co 2p1/2 from
18
CoOx, which is the product of the oxidation of cobalt on the surface of the sample by air [26, 27].
19
Two shake-up satellites appear at 786.3 and 802.2 eV [26]. Compared to CoSb2 (777.9 and 792.7
20
eV for metallic Co), it is observed that the characteristic peaks of metallic Co for Sb/CoSb2@C
21
shift to a higher binding energy, indicating a decreased electron cloud density around CoSb2. The
22
electron cloud bias from CoSb2 to Sb is solid evidence of enhanced interaction and strong 8
1
coupling between CoSb2 and Sb. Fig. 3c shows the high-resolution spectra of C 1s, which consist
2
of three main peaks at 284.8, 285.5 and 287.4 eV corresponding to the C–C, C–N, C–O species,
3
respectively [28]. The C 1s spectra of N-doped carbon derived from annealed polydopamine
4
shown in Fig. S4 exhibited three peaks at 284.8, 285.8 and 287.9 eV, which were similar with the
5
C 1s spectra of Sb/CoSb2@C. The N 1s spectra (Fig. 3d) exhibit two peaks at 398.6 and 400.3 eV,
6
which can be assigned to pyridinic N and pyrrolic N, respectively [28-30]. In addition, the carbon,
7
nitrogen, antimony and cobalt content on the surface of the sample measured by XPS was 92.6,
8
5.5, 1.4 and 0.5 atom%, respectively. The signals of carbon, nitrogen, antimony and cobalt on the
9
surface of the Sb/CoSb2@C sample can also be clearly identified in the energy dispersive
10
spectrum (Fig. S5), confirming their existence in Sb/CoSb2@C sample. The analyses of XRD,
11
XPS and EDS suggest that metallic Sb, CoSb2 and nitrogen doped carbon exist in the
12
as-constructed sample.
13
To determine the accurate component contents in the Sb/CoSb2@C sample, TGA was
14
conducted in nitrogen and the air (Fig. S6). The weight loss (27.8%) of the Sb/CoSb2@C sample
15
measured by thermogravimetric test in nitrogen mainly comes from the heat evaporation of
16
metallic antimony due to its lower melting point (630 °C) [31]. After deducting the weight loss of
17
the heat evaporation of metallic antimony, TGA curve of the Sb/CoSb2@C sample in the air
18
unravels that the weight contents of C, Sb and Co in Sb/CoSb2@C sample are about 40.7-41.7%,
19
48.1-59.3% and 0-10.2 wt%, respectively [31-33].
20
The SEM images (Fig. 4a-b) reveal that both the CoSb-S precursor and the Sb/CoSb2@C
21
sample show particle morphology, and the precursors exhibit larger diameters. EDS elemental
22
mapping results (Fig. S7) show the distribution of Sb, C, Co, and N in the Sb/CoSb2@C sample. 9
1
To further reveal the microstructure, TEM images are displayed in Fig.4c-d. As shown in Fig. 4c,
2
the Sb and CoSb2 nanoparticles are embedded into the N-doped carbon nanoparticles, which show
3
amorphous structures (Fig. 4d). The lattices of the Sb and CoSb2 are observed in Fig. 4e-f, in
4
which the marked d-spacing of 0.175 nm and 0.254 nm correspond well to the (202) plane of Sb
5
and the (-212) plane of CoSb2, respectively. The SEM images (Fig. S8a-b) reveal that both the
6
CoSb-S precursor and the Sb@C sample show nanosphere-like morphology with the uniform size,
7
and the precursors also display larger diameters. The BET surface areas of the Sb@C sample and
8
the Sb/CoSb2@C sample are 10.2 and 12.0 m2 g-1 according to the adsorption-desorption data (Fig.
9
S9a), respectively. And the more micropores and mesopores in the Sb/CoSb2@C sample was
10
shown in Fig. S9b.
11
The electrochemical performances of the Sb/CoSb2@C electrode, Sb@C electrode and
12
Sb/CoSb2 electrode for LIBs are measured by CV and galvanostatic charge/discharge tests. In the
13
CV curves of Sb/CoSb2@C electrode (Fig. 5a), the cathodic scan of the first cycle displays that
14
two cathodic peaks at ~0.7 and 0.8 V are attributed to alloying processes of Sb from metallic Sb
15
and CoSb2 with Li, which contains the two phase transitions of Sb into Li2Sb and Li2Sb into Li3Sb
16
[34, 35]. And the weak peak at ~0.4 V demonstrates the formation of solid electrolyte interphase
17
film [36]. The cathodic peak at 1.2 V corresponds to the delithiation reactions of Li3Sb [35]. In the
18
next four cycles, the peaks are basically overlapped, indicating good reversibility of these
19
reactions of Sb/CoSb2@C electrodes. The CV curves of Sb@C electrode (Fig. 5b) show the
20
similar trends except for the different cathodic peak at 1.3 V in the first cycle, which may be
21
attributed to the decomposition of SbOx [37-39]. The CV curves of CoSb2 electrode (Fig. S10)
22
exhibited one cathodic peak at ~0.8 V, and the sharp peak at ~0.3 V arises from the formation of 10
1
solid electrolyte interphase film. In the next four cycles, there are lower intensity of both cathodic
2
and anodic peaks, reflecting that the conversion reaction is not completely reversible, which may
3
be leads to irreversible capacity loss and lower coulombic efficiency. In addition, the curves of
4
Sb@C and Sb/CoSb2 electrodes in the next cycles show imperfect overlaps, indicating the inferior
5
reversibility of Sb@C and Sb/CoSb2 electrodes. The initial three charge and discharge curves of
6
these two composites are shown in Fig. S11a-b. There are the voltage plateaus in these curves,
7
which correspond well to the results of the CV analysis.
8
Fig. 5c and Fig S12 shows the electrochemical performances of Sb@C and Sb/CoSb2@C
9
electrodes at the current densities from 0.1 A g−1 to 5 A g−1, respectively. The electrode capacity
10
was stable at about 958.7 mAh g−1 at 0.1 A g−1, which is close to its theoretical capacity. Even at
11
the high current density of 5 A g−1, the Sb/CoSb2@C electrodes still keep the discharge platform
12
well, which conformed that the present of CoSb2 can efficiency enhance ion/electron transmission.
13
Fig. 5d and Fig. S13 show the rate capability of the Sb/CoSb2@C electrode, the Sb@C electrode
14
and the Sb/CoSb2 electrode at current densities from 0.1 to 10 A g−1. At increasing current
15
densities of 0.1, 0.2, 0.5, 1, 2, 5, 8 and 10 A g−1, the Sb/CoSb2@C electrode delivers the average
16
discharge capacities of 958.7, 864.2, 797.9, 730.4, 647.0, 485.4, 368.8 and 320.2 mAh g−1,
17
respectively. The Sb@C electrode delivers inferior average specific capacities of 889.9, 691.8,
18
572.5, 482.5, 77.2, 36.0 and 31.7 mA h g−1 at 0.1, 0.2, 0.5, 1, 2, 5, 8 and 10 A g−1, respectively,
19
The capacity of Sb/CoSb2@C electrode maintains at a high value when the current density returns
20
to 0.1 A g−1, indicating the good rate capability of Sb/CoSb2@C. Compared to Sb/CoSb2@C
21
electrode, the discharge capacity based on Sb/CoSb2 electrode (Fig. S13) decreases rapidly at
22
current densities of 0.1, 0.2, 0.5, and 1 A g−1, it is noted that the capacity is around 20 mA h g−1 at 11
1
5, 8, and 10 A g−1, this result indicated high stability of Sb/CoSb2@C electrode by polydopamine
2
coating [40]. Consistent conclusion can be reached by the cycling performances. As displayed in
3
Fig. 5e, the Sb/CoSb2@C electrode and the Sb@C electrode exhibit that the charge capacities
4
were maintained at 878.2 and 656.9 mAh g−1 after 500 cycles, respectively. Specially, the
5
Sb/CoSb2@C electrode and the Sb@C electrode retain high coulombic efficiencies of 99.6% and
6
99.1% over 500 cycles, respectively. The Sb/CoSb2 electrode (Fig. S14) delivers an initial specific
7
capacity of ∼825 mA h g−1 but it can maintain a capacity of 99 mA h g−1 after 350 cycles. The
8
electrochemical property of the Sb/CoSb2 electrode seems to be much inferior to that of the
9
Sb/CoSb2@C electrode. It is worth noting that the capacity decays rapidly during the initial 100
10
cycles for the Sb/CoSb2 electrode, which might be ascribed to the formation of unstable SEI film
11
during the repeated lithium ion insertion/extraction due to the lack of conductive carbon outer
12
layer [40]. These electrochemical performance results illustrate the outstanding specific capacity
13
and high cycle stability of the Sb/CoSb2@C electrode. The electrochemical impedance
14
spectroscopy (EIS) measurements of the Sb/CoSb2@C, Sb@C and Sb/CoSb2 electrode before and
15
after cycling were analyzed and shown in Fig. S15a-b. The Sb/CoSb2@C and Sb@C composite
16
electrode exhibit a lower interface impedance than that of the Sb/CoSb2 electrode, indicating
17
improved interfacial properties by introduced carbon out layer, leading to faster charge transfer
18
across the electrode/electrolyte interface. [40] In addition, the linear slope of the Sb@CoSb2@C
19
composite electrode in the low frequency region is higher than that of the Sb@C electrode,
20
suggesting superior Li-ion diffusion of Sb/CoSb2@C. Apart from that, the Sb@CoSb2@C
21
composite electrode exhibits a lower ohmic resistance shown in the enlarged part of Fig. S15a,
22
indicating the higher electronic conductivity of Sb@CoSb2@C composite. As shown in Fig. S15b, 12
1
the electrode resistance of all electrodes are increased after cycling, which are mainly attributed to
2
the formation of SEI film. The Sb/CoSb2@C composite electrode show the highest linear slope
3
compared to the other electrodes, indicating the better electrode kinetics and electrochemical
4
properties of the Sb/CoSb2@C electrode.
5
To further understand the better cycle stability for the Sb/CoSb2@C anode, the morphologies
6
of Sb/CoSb2@C and Sb/CoSb2 after 100 cycles at 1 A g-1 were studied. As shown in Fig. S16a, the
7
structure of the lithiated Sb/CoSb2 electrode was seriously destructed, which changed to irregular
8
chunky particles aggregated by isolated nanoparticles. However, the spherical nanostructure of
9
Sb/CoSb2@C was largely maintained, indicating the relatively higher structural stability to a great
10
extent due to the effective strain/stress accommodation of the resilient carbon layer.
11
Conclusions
12
In conclusion, a new type of nitrogen-doped carbon sphere encapsulating antimony-cobalt
13
antimony binary nanoseeds has been synthesized by annealing the nanospheres containing
14
antimony and cobalt, and Sb/CoSb2@C composites could be employed as a novel composite
15
anode material for LIBs with outstanding specific capacity and extremely high cycle stability.
16
Compared with Sb@C electrode (31.7 mA h g−1) and Sb/CoSb2 electrode (20 mA h g−1), the
17
as-synthesized Sb/CoSb2@C electrode exhibit the excellent charge/discharge rate capability of
18
320.2 mAh g−1 at 10.0 A g−1. More remarkably, the high specific capacity of 878.2 mAh g−1 for
19
LIBs with Sb/CoSb2@C electrode can be well-maintained after 500 cycles at 1 A g−1. The
20
excellent Li-ion storage properties can be attributed to the incorporation with CoSb2 and
21
nitrogen-doped carbon matrix, which not only guarantees the high electronic conductivity, but
22
could effectively alleviate the volume changes during cell cycling. Our work demonstrates an 13
1
integrated design of antimony/cobalt-antimony/N-doped carbon composites, which may provide
2
some inspiration for functional materials with improved lithium-ion storage performances.
3
Acknowledgement
4
This work was supported by the National Natural Science Foundation of China (No.
5
51672146, 21805157, 51972187), the Natural Science Foundation of Shandong Province
6
(ZR2018BEM011, ZR2019MEM043 and ZR2019MB037), the Key R & D project of Shandong
7
Province (2019GGX103034) and the Development Program in Science and Technology of
8
Qingdao (19-6-2-12-cg).
9
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Figure captions
19
Fig. 1 Schematic illustration of the preparation of the Sb/CoSb2@C sample.
20
Fig. 2 XRD patterns of the Sb/CoSb2@C sample (a, b) and the Sb@C sample (c).
21
Fig. 3 High-resolution XPS of the Sb 3d (a), Co 2p (b), C 1s (c) and N 1s (d) in the Sb/CoSb2@C
22
sample. 19
1
Fig. 4 The SEM images of CoSb-S precursor (a), Sb/CoSb2@C sample (b). TEM image of
2
Sb/CoSb2@C sample (c-d). HRTEM lattice image of Sb@C and Sb/CoSb2@C sample (e-f).
3
Fig. 5 The CV curves of the Sb/CoSb2@C electrode (a) and the Sb@C (b) electrode for LIBs at
4
the initial five cycles. (c) The charge/discharge profiles from 0.1 to 5 A g−1 of the Sb/CoSb2@C
5
electrode. The rate performances of the Sb/CoSb2@C electrode and the Sb@C electrode at various
6
current density (d). The cycling performances of the Sb/CoSb2@C electrode and the Sb@C
7
electrode at current density of 1 A g−1 (e).
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 20
1 2 3
Figure 1
4 5
6 7 8 9
Figure 2
10 11
12 21
1 2 3
Figure 3
4
5 6 7 8 9 10 11 12 22
1 2 3 4
Figure 4
5 6
7 8 9 10 11 12 13 14 15 16 23
1 2 3
Figure 5
4
5
24
Highlights The Sb/CoSb2@C is designed combine polydopamine coating and annealing method CoSb2 and nitrogen-doped carbon matrix guarantees the high electronic conductivity The Sb/CoSb2@C composite exhibit the excellent charge/discharge rate capability Sb/CoSb2@C composite could be a promising anode for advanced lithium-ion batteries
Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.