[email protected] spheres with enhanced electrochemical performance for lithium ion storage

Accepted Manuscript Partially Reduced Sb/Sb2O3@C spheres with Enhanced Electrochemical Performance for Lithium Ion Storage Xia Yang, Jingjing Ma, Huijun Wang, Yaqin Chai, Ruo Yuan PII:

S0254-0584(18)30289-X

DOI:

10.1016/j.matchemphys.2018.04.027

Reference:

MAC 20522

To appear in:

Materials Chemistry and Physics

Please cite this article as: Xia Yang, Jingjing Ma, Huijun Wang, Yaqin Chai, Ruo Yuan, Partially Reduced Sb/Sb2O3@C spheres with Enhanced Electrochemical Performance for Lithium Ion Storage, Materials Chemistry and Physics (2018), doi: 10.1016/j.matchemphys.2018.04.027 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. 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.

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Partially Reduced Sb/Sb2O3@C spheres with Enhanced Electrochemical Performance for Lithium Ion Storage Xia Yang*, Jingjing Ma, Huijun Wang, Yaqin Chai, Ruo Yuan* Key Laboratory of Luminescent and Real-Time Analytical Chemistry (Southwest

Southwest University, Chongqing 400715, PR China Abstract

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University), Ministry of Education, College of Chemistry and Chemical Engineering,

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Antimony (Sb) based materials, as anode for lithium ion batteries (LIBs), exhibit a

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great potential these years. However, its actual application is restricted by the quick capacity loss due to the volume change during cycling process. In this work, we have developed a simple solvothermal and partial thermal reduction process to synthesize the carbon-coated Sb/Sb2O3 (Sb/Sb2O3@C) sphere, which can enhance the

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electrochemical performance of Sb based anode for lithium ion batteries. When served as anode material for LIBs, the Sb/Sb2O3@C sphere can exhibit an excellent electrochemical performance with a high specific capacity of 686 mAh g-1 at the

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current density of 100 mA g-1 and superior rate reversibility. Even tested at a larger

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current density of 500 mA g-1, the electrode can still maintain a good capacity of 467 mAh g-1 after 95 cycles. This design involved partial reduction can effectively improve the cycling performance and rate capability. The results indicate that the Sb/Sb2O3@C sphere could be a potential candidate as anode material for LIBs. Keywords: Lithium ion batteries; Sb/Sb2O3@C sphere; Partial reduction

* Corresponding author. E-mail address: [email protected] (X. Yang); [email protected] (R. Yuan). 1

ACCEPTED MANUSCRIPT 1. Introduction Lithium ion batteries (LIBs) are popular as portable electronic devices. [1,2] The ever-increasing need for high-performance electrode materials has been a famous

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topic. [3,4] However, commercial graphite cannot be satisfied with the requirements owing to its limited theoretical capacity (370 mAh g-1). [5,6] Some metal-based anode materials (such as Sb, Sn, Si, etc.) come into our sight and gain lots of attentions on

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LIBs or sodium ion batteries (SIBs). Among that, Sb was one kind of important anode

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materials, which is attributed to its decent kinetic characteristics and high theoretical capacity (660 mAh g-1) for LIBs. [7-9] However, the problem of using pure Sb as anode is the poor cyclic performance. [10-12]

To alleviate the problem, many attempts have been done in published works. One

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approach is combining Sb with other metals to form alloy materials. [13-16] For example, Ni-Sb intermetallic material has exhibited its advantages for LIBs and SIBs. [17] Sb2Te3 has been designed as electrode material by high-energy ball milling. [18]

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Furthermore, combining Sb with conductive carbonaceous materials is another way.

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Wang’ group reported that Sb/C fibers can be used as an efficient electrode material for SIBs. [19] Cho’ team has synthesized hollow Sb particles through SiO2 template. [20] Although the above approaches can mitigate the problems of Sb electrode to some extent, some shortages are still non-ignorable (such as the complicated synthesis process, the irregular morphology). According to references, composite of metal/metal-based oxide can solve the problem of the quick capacity loss. [21,22] Inspired by this, we chose a simple and scalable partial reduction process [23] to 2

ACCEPTED MANUSCRIPT prepare partially reduced carbon-coated Sb2O3 spheres (named as Sb/Sb2O3@C) to improve Sb based lithium ion batteries. In this study, a facile solvothermal process was used to obtain the regular spheres

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precursor. After a carbon-coating and further partial reduction, the Sb/Sb2O3@C spheres were synthesized. As anode material for LIBs, both of the cyclic property and rate capacity can be dramatically enhanced for the Sb/Sb2O3@C spheres. This work

2. Experimental 2.1 Materials synthesis

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based materials and other metal oxide materials.

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employing partial reduction method may provide one approach for enhancing Sb

2 mmol SbCl3 was dissolved into 40 mL of absolute ethanol under stirring to

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form a transparent solution. Then the above solution was shifted to 50 mL stainless-steel autoclave maintained at 160 oC for 15 h. After that, the Sb4O5Cl2 precursor (abbreviated as SbOCl) was obtained with centrifugation, washed with

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ethanol several times and dried under 60 oC for 12 h. Then 100 mg of the product was

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added into the 80 mL of Tris-buffer solution (pH = 8.5) under ultrasonic treatment. Then, 50 mg of dopamine was mixed into the solution under stirring for 5 h. Nextly, the precipitates were obtained with centrifugation, washed several times by ethanol and dried. At last, the product was annealed at 350 oC for 2 h with H2 atmosphere to synthesize the Sb/Sb2O3@C sphere. 2.2 Materials Characterization The X-ray diffraction (XRD) pattern was tested by MAXima 7000 (Shimadzu, 3

ACCEPTED MANUSCRIPT Japan) with Cu Kα radiation. Raman microscopy was carried on Invia Reflex (Renishaw, UK). The morphology of products was identified on scanning electron microscope (SEM) by Philips XL30FEG SEM (Eindhoven,

Netherlands).

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Transmission electron microscopy (TEM) was carried on JEM-2100 (JEOL, Japan) for the inner structure. X-ray Photo-electron Spectroscopy (XPS, Thermo Scientific Escalab 250Xi, USA) was tested to verify the valence of the materials.

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Thermogravimetric analysis (TGA) was obtained by using Q600-SDT (TA

2.3 Electrochemical Measurements

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Instruments, USA) under a flow of air.

For electrode preparation, the synthesized material, carbon black and binder (sodium carboxymethyl cellulose) were mixed with the weight ratio of 7:2:1. 1 mol

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L-1 LiPF6 in ethylene carbonate/diethyl carbon (1:1 in volume) was used as electrolyte. Celgard 2300 and lithium metal were employed as separator and counter electrode respectively. Cyclic voltammetry (CV) test was measured on CHI 660B within the

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voltage scope of 0.005-3.0 V. The electrical conductivity of products was determined

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on electrochemical impedance spectroscopy (EIS) via CHI 660D with frequency from 0.1 Hz to 1.0×105 Hz. The electrochemical performance of Sb/Sb2O3@C sphere was tested on Land CT2001A within a voltage window of 0.005-3.0 V. 3. Results and discussion The preparation mechanism of Sb/Sb2O3@C sphere was exhibited in Scheme 1. Firstly, the SbOCl sphere was prepared by a scalable solvothermal method. Secondly, self-polymerized dopamine (PDA) was formed on the surface of the SbOCl sphere to 4

ACCEPTED MANUSCRIPT obtain the SbOCl/PDA composite. Finally, after annealing, the SbOCl/PDA sphere was decomposed to form the Sb2O3, which was partially reduced to the element Sb by H2 atmosphere at the same time. In this step, PDA was carbonized as the coating layer

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by the same procedure without using PDA.

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to form Sb/Sb2O3@C sphere. The preparation mechanism of Sb/Sb2O3 was prepared

Scheme 1. Schematic illustration of synthesis of the Sb/Sb2O3@C sphere.

The X-ray powder diffraction (XRD) of Sb4O5Cl2 (abbreviated as SbOCl) was shown in Figure 1a, which was corresponding to the JCPDS Card NO. 70-1102. The

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crystal structure of the Sb/Sb2O3@C was determined by XRD test in Figure 1b. These characteristic peaks were indexed to the Sb phase (JCPDS Card NO. 35-0732) and

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Sb2O3 phase (JCPDS Card NO. 11-0689). In Raman spectra (Figure 1c), the distinct band at around 144 cm-1 was attributed to Sb. [22] Four peaks at 189, 251, 371 and

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451 cm-1 were also observed, which belonged to the Sb2O3. [24] Two peaks of D-band and G-band at about 1351 cm-1 and 1572 cm-1 respectively indicated the characteristic of carbon in the composite. [25] X-ray photoelectron spectroscopy (XPS) of Sb/Sb2O3@C sphere was analyzed in Figure 1d. The fitted two peaks for Sb 3d located at 530.2 and 540.0 eV, which were associated with Sb (III) of Sb2O3. Another two peaks at 529.2 and 538.5 eV were accorded with Sb (0) [24]. This results further indicated the existence of Sb. To analyze the carbon content of the Sb/Sb2O3@C 5

ACCEPTED MANUSCRIPT sample, thermal gravimetric analyzer (TGA) tests were collected by the Figure 1e. The TG curves of Sb/Sb2O3@C sample was tested under a flow of air at 800 oC with the temperature rate of 10 oC min-1. It is known that C would all transformed into CO2

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under high temperature. Therefore, the final pyrolysis product was made up of Sb2O3, which possessed a weight content of 82.2 wt % (Figure 1e). So, based on the TG data analysis, we could calculate the weight percentage of C in the Sb/Sb2O3@C materials

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was 11.2 %.

Figure 1. (a-b) XRD patterns of SbOCl and Sb/Sb2O3@C sphere. (c) Raman spectra of the

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Sb/Sb2O3@C sphere. (d) The XPS spectra of Sb 3d for Sb/Sb2O3@C sphere. (e) The TG curve of the Sb/Sb2O3@C sphere.

Scanning electron microscopy (SEM) images are shown in Figure 2, the obtained

SbOCl reveals a regular sphere shape (Figure 2a) with a size of 0.5~1 µm. After PDA coating, the morphology was displayed in Figure 2b, which almost keep the same shape as Figure 2a. Through high-temperature process (Figure 2c), the generated Sb/Sb2O3@C can still keep the similar structures. Transmission electron microscopy

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ACCEPTED MANUSCRIPT (TEM) image presented the refined structure of Sb/Sb2O3@C sphere (Figure 3a). It can be clearly observed from Figure 3b that the thickness of carbon layer is approximately 10 nm. As shown in Figure 3c-d, the HRTEM images exhibit the

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crystal lattices of Sb and Sb2O3. The interplanar distances of 0.30 nm and 0.32 nm conform to the (012) plane of Sb (JCPDS Card NO. 35-0732) and the (121) plane of

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Sb2O3 (JCPDS Card NO. 11-0689), respectively.

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Figure 2. (a-c) SEM images of the SbOCl sphere, SbOCl/PDA sphere and Sb/Sb2O3@C sphere.

Figure 3. (a-b) TEM and (c-d) HRTEM images of the Sb/Sb2O3@C sphere.

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ACCEPTED MANUSCRIPT The electrochemical property of Sb/Sb2O3@C sphere was tested by cyclic voltammogram (CV) at scan rate of 0.5 mV s-1 within a voltage range of 0.005-3.0 V (Figure 4a). In the 1st cycle, two cathodic peaks appeared at 0.6 and 1.1 V, which were associated with the formation of solid electrolyte interface (SEI) film and the

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transformation of Sb/Sb2O3 to LixSb, LixO and Sb. [26-28] In the subsequent cathodic reactions, the reduction peaks shifted to 0.7 and 1.5 V. This phenomenon can be explained as an irreversible reaction to a small amount of active material during the Li+

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imbedding/deembedding process and partial insertion of Li+ into the Sb/Sb2O3 to produce LixSb [7, 26]. In the 1st anodic scan, the peaks at around 1.2 and 1.4 V were observed,

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which indicated the de-alloying procedure of LixSb and decomposition of LixO. [7] Except the 1st cycle, all the curves overlapped very well, which showed the stable electrochemical properties of Sb/Sb2O3@C sphere. Figure 4b depicted the discharge/charge curves of Sb/Sb2O3@C sphere at the current density of 100 mA g-1

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for different cycles. In the first cycle, a high discharge and charge capacity of 1310 and 1249 mAh g-1 were delivered respectively, leading to a coulombic efficiency of 95.3%. Then the capacity decreased in the following cycles. The capacity loss was

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due to solid electrolyte interface (SEI) film and decomposition of electrolyte. [29,30]

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Figure 4. (a) CVs of the Sb/Sb2O3@C sphere with a potential of 0.005-3.0 V at a scan rate of 0.5 mV s-1. (b-c) Discharge/charge curves and cycling performance of the Sb/Sb2O3@C sphere at the current density of 100 mA g-1. (d) Cycling performance of the Sb/Sb2O3@C sphere at 500 mA g-1(The current density of the first five cycles is 100 mA g-1).

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The cyclic performance of the electrode material was operated under current density of 100 mA g-1 in Figure 4c. After 100 cycles, the Sb/Sb2O3@C electrode maintained a superior discharge and charge capacity of 686 and 684 mAh g-1,

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respectively, delivering a high coulombic efficiency of 99.7%. Such a good stable

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cycling property can be owing to the fine conductivity and structure of material to alleviate the volume change in the lithiation/delithiation process. At the current density of 500 mA g-1 (Figure 4d), the discharge and charge capacity can retain an advantageous value of 467 and 459 mAh g-1 respectively after 95 cycles with a coulombic efficiency of 98.2 %. Rate features of Sb/Sb2O3@C sphere were shown in Figure 5a. When setting the current densities as 100, 200, 500 and 1000 mA g-1, stable capacities of 1219, 780, 9

ACCEPTED MANUSCRIPT 614 and 465 mAh g-1 was exhibited respectively. When cycled again at the current density of 100 mA g-1, the capacity retained a high capacity of 743 mAh g-1. The Nyquist plot and simulated results of Sb/Sb2O3@C electrode at the frequency window

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of 0.1 Hz-1.0 × 105 Hz were shown in Figure 5b. Rs was the electrolytes resistance in the intercept of high-frequency in axis. Rct represented the charge-transfer resistance at high-frequency intercept for the charge-transfer process between the interface of

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electrolyte and electrode. [31-33] From the data of equivalent circuit fitting, the value

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of Rct was 63 Ω. Such a superior electric conductivity increased the transmission speed of Li+ during the discharge/charge process to further improve the

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electrochemical performance of Sb/Sb2O3@C sphere as anode material for LIBs.

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Figure 5. (a) Rate capacity of the Sb/Sb2O3@C sphere. (b) Experimental and simulated Nyquist plot of the Sb/Sb2O3@C electrode. The inset of (b) is equivalent circuit.

We have compared the electrochemical properties of Sb/Sb2O3 and Sb/Sb2O3@C

materials prepared by the same method, as shown in Figure 6a. From the image, the Sb/Sb2O3@C spheres behaved better reversible capacity with ~300 mAh g-1 than Sb/Sb2O3@ sample (~100 mAh g-1) at high current density of 1000 mA g-1 after 60 cycles. Hence, it can be found that the electrochemical properties of carbon coated

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ACCEPTED MANUSCRIPT materials are obviously higher than those without carbon coated materials. To study the structure stability of the Sb/Sb2O3@C, the SEM image indicated that the Sb/Sb2O3@C mainly retained primary morphology after 100 cycles at the current

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density of 100 mA g-1 (Figure 6b).

Figure 6. (a) Cycling performance of the Sb/Sb2O3@C and Sb/Sb2O3 samples at 1000 mA g-1. (b) SEM image of the Sb/Sb2O3@C sphere after 100 cycles at the current density of 100 mA g-1.

4. Conclusion

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In conclusion, we have successfully designed a simple preparation of Sb/Sb2O3@C sphere through partial reduction. Benefiting from partially reduced structure and good conductivity, the Sb/Sb2O3@C sphere electrode displayed good

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cyclability. This Sb/Sb2O3@C material also can mitigate the volume collapse during

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the Li+ insertion/extraction to improve its stability in the cycling. Such the smart design and facile synthesis developed in this work can be an effective way to significantly improve the electrochemical performance of other electrode material. Acknowledgements

This work was supported by the NNSF of China (51602263, 51473136, 21575116), the Fundamental Research Funds for the Central Universities (XDJK2015C099,

SWU114079),

China

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Postdoctoral

Science

Foundation

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2016T90827)

and

Chongqing

Postdoctoral Research

Project (xm2015019). References

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Highlight The Sb/Sb2O3@C spheres were synthesized through a partial reduction method.

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This design can buffer structure expansion during discharge/charge process.

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The Sb/Sb2O3@C spheres behaved good electrochemical performance.

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