Facile Synthesis of Carbon-Coated Porous Sb2Te3 Nanoplates with

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Facile Synthesis of Carbon-Coated Porous Sb2Te3 Nanoplates with High Alkali Metal Ions Storage Wudi Zhang, Qianyu Zhang, Qiufan Shi, Sen Xin, Jiang Wu, Chuan-Ling Zhang, Lifeng Qiu, and Chaofeng Zhang ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.9b09056 • Publication Date (Web): 22 Jul 2019 Downloaded from pubs.acs.org on July 23, 2019

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ACS Applied Materials & Interfaces

Facile Synthesis of Carbon-Coated Porous Sb2Te3 Nanoplates with High Alkali Metal Ions Storage Wudi Zhang,† Qianyu Zhang,‖ Qiufan Shi,† Sen Xin,⁑ Jiang Wu,‡ Chuan-Ling Zhang,*,† Lifeng Qiu,† Chaofeng Zhang*,§ †

School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei, Anhui 230009, P. R. China ‖ Department of Materials Science and Engineering, Dongguan University of Technology, Songshan Lake, Dongguan, Guangdong 523808, P. R. China § Institutes

of Physical Science and Information Technology, Anhui University; Key Laboratory of Structure and Functional Regulation of Hybrid Material (Anhui University), Ministry of Education, Hefei, Anhui 230601, P. R. China ⁑ Institute

of Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China Key Laboratory for Tibet Plateau phytochemistry of Qinghai Province, College of Pharmacy, Qinghai Nationalities University, Xining, Qinghai 810008, P. R. China ‡

ABSTRACT Constructing advanced anode materials with suitable operational potential and high energy density towards metal ion batteries is of significance for next-generation batteries. Carbon-coated porous Sb2Te3 nanoplates with high density and suitable operational potential, prepared by a hydrothermal and carbonization technique, manifests good electrochemical performance, including excellent rate capability, high capacities, and outstanding cycling performance. This performance can be traced to its special structure, including porous Sb2Te3 and the shell of carbon, which can provide fast charge transfer paths and maintain the structural stability for the entire material. The proposed strategy here of embedding porous high-density anode material in twodimensional carbon provides a new avenue for designing anode materials with excellent gravimetric and volumetric capacities towards superior energy storage. KEYWORDS: volumetric capacity, porous Sb2Te3@C, lithium ion batteries, Sb2Te3, 1

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sodium ion batteries, nanoplates

INTRODUCTION Lithium ion batteries (LIBs) have held dominant position in the energy storage market for potable electronics and shown great potential in electric vehicles (EVs).1-7 Currently, graphite and Li4Ti5O12 are successfully applied in commercial LIBs. However, graphite possesses a low operational potential, which is close to that for Li plating, resulting in the growth of lithium dendrites and safety concerns. Also, the volumetric capacity of graphite is limited due to its low density.8-9 The other one, Li4Ti5O12, can avoid the Li plating because of its high operational potential of 1.55 V and feature of “zero-strain” during cycling.10-11 Its low capacity and high potential vs. Li/Li+, however, would inevitably result in the low energy density of Li4Ti5O12-containing battery. It is essential to exploit an anode material with high volumetric/gravimetric capacity and suitable potential, when considering the growing demands for safety and the miniaturization of batteries.8-9, 12 Recently, antimony-based materials are attracting growing attention as promising electrode materials for batteries for a variety reasons, including their suitable response potential, high density, and high theoretical capacity.13-17 Sb2Te3 has a much greater density (6.66 g/cm3) than other Sb-based materials, including Sb2Se3, Sb2S3, and Sb2O3.13 That means that Sb2Te3, notionally at least, possesses a large theoretical capacity (3419 mAh cm−3).13 Additionally, Te has a higher conductivity (2×10−4 mS m−1) than S or Se.18 Te can react with Li by forming Li2Te (420 mAh/g, 2621 2


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mAh/cm3).18-20 These advantageous features make it attractive to anode with high energy density and suitable potential plateau. Remarkably, the rational design of a proper electrode materials can dramatically enhance the electrochemical performance of batteries.7, 21-22 The two-dimensional (2D) materials show fascinating physical and electronic properties.23-25 For example, the electron confinement in two dimensions endows 2D materials with naturally superior electronic properties, large specific surface area, and high anisotropy, which give them excellent electrochemical and mechanical properties, and offer great opportunities for developing 2D material-based electrodes for batteries.24 Carbon coating would be an effective method to eliminate the direct contact between electrode materials and electrolyte during cycling.26-32 Also, the porous structure is a useful framework in alleviating the volume changes during charging/discharging for batteries.33-34 As an alternative to LIBs, sodium ion batteries (SIBs) are receiving growing attention for the widespread availability and low cost of sodium resources.35-37 The development of electrode materials with large volumetric/gravimetric capacity and suitable potential plateau is also crucial to the success of SIBs. Herein, we designed and prepared a 2D carbon-coated porous Sb2Te3 nanoplates (Sb2Te3@C) by a facile hydrothermal and carbonization strategy. In the unique design, porous Sb2Te3 nanoplates are compactly encapsulated by a uniform carbon layer, which can effectively relieve structural stress and prevent structural pulverization, thus meeting the challenge brought about by large volume changes, and stabilizing the solid electrolyte interface (SEI) film. As expected, with this optimal design, the Sb2Te3@C 3



sample shows good Li/Na storage performance. EXPERIMENTAL SECTION Synthesis of Sb2Te3 Nanoplates. The Sb2Te3 nanoplates were synthesized using a hydrothermal method.38 Typically, 0.400 g tartaric acid and 0.100 mmol SbCl3 were dissolved in about 5 mL distilled water (DIW). Then, 20 mL ammonia (25% ~ 28%), 0.140 mmol of Na2TeO3, and 8 mL H4N2·H2O (85%) were added to the above solution, respectively. After stirring, this solution was transferred to a 40 mL Teflon-lined autoclave, which was then kept at 180 ℃ for 5 hours. The product was obtained by centrifuging and washing with water and ethanol before drying at 60 ℃ under vacuum conditions. Synthesis of Sb2Te3@C. The preparation process of the Sb2Te3@C nanoplates can be found in the Figure S1. 30 mg Sb2Te3 nanoplates were dispersed in 15 mL ethanol and 10 mL DIW under ultrasonication for 15 min. Then, 23 mg hexadecyl trimethyl ammonium bromide (CTAB) was added to the dispersive solution with stirring. 10 min later, 60 µL NH3·H2O and 0.015g resorcinol were added into this solution, respectively. Afterwards, 12.5 µL of formaldehyde was added dropwise to this solution. After stirring for 18 h, Sb2Te3@resorcinol-formaldehyde resin (Sb2Te3@RF) was collected by centrifugation and washing with DIW and ethanol. Finally, Sb2Te3@C was obtained after calcination under Ar at 700 ℃ for 3 h. Materials Characterization. Samples were studied using X-ray diffraction (XRD, GBC MMA, Cu Kα), a transmission electron microscopy (TEM equipped with SAED, JEM-2011F), a field-emission scanning electron microscopy (FESEM, JEOL JSM4


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7500FA). Element distributions images were obtained with an X-ray spectrometer connected to TEM. Tap density was characterized using a tap density tester (BT-301, Bettersize). The thermal properties were obtained by thermal analyzer (TAI/DSC Q2000) with a rate of 10 °C/min under flowing air. N2 sorption isotherms were collected using Autosorb AS-6B (Quantachrome). Raman result was collected using a Jobin Yvon HR800. Electrochemical characterizations. The working electrode was made by mixing the material, polyvinylidene difluoride and Super P in a weight ratio of 8:1:1. The electrolyte for LIBs is 1 M LiPF6 in ethylene carbonate/dimethyl carbonate (volume ratio = 1:1). Similarly, the electrolyte for SIBs is 1 M NaPF6 in ethylene carbonate/diethyl carbonate (volume ratio = 3:7) with 5 vol% fluoroethylene carbonate. Electrochemical impedance (EIS) and cyclic voltammetry (CV) were conducted using an electrochemical workstation (CHI 760D). The cells were galvanostatically cycled over a voltage range of 0.01-3 V (Land Battery System). RESULTS AND DISCUSSION The structure was first investigated by FESEM and TEM. As shown in Figure S2, the as-prepared Sb2Te3 can be observed to be uniform with hexagonal-based plates of welldefined shape. Further RF coating on the Sb2Te3 nanoplates results in an increased thickness, as depicted in Figure S3a-b. The structural feature of Sb2Te3@RF was elucidated by TEM analysis. The images in Figure S3c-d manifest a well-defined and intact hexagonal-based structure of Sb2Te3@RF. The interplanar distance of 0.315 nm (Figure S3f) obtained from a selected area (Figure S3e) is corresponding to the d5



spacing of (015) planes of hexagonal Sb2Te3 (JCPDS No.71-0393). After carbonization, the structure of the nanoplates is perfectly maintained (Figure 1a). The thickness of carbon shell is in the range of 50-80 nm (Figure 1b-c). Additionally, a porous structure can be found (Figure 1b-c). To understand the formation of the porous structure, we repeated the synthesize process of Sb2Te3@RF from Sb2Te3 without adding the precursors of resorcinol and formaldehyde. The morphology of the obtained sample was investigated by TEM and SEM. As shown in Figure S3g-i, the porous structure can be clearly observed. It means that the porous structure of Sb2Te3 can be formed in the solution including CTAB and ammonia. The representative HRTEM images of the sample Sb2Te3@C in Figure 1d-e show the existence of (015) and (110) crystal planes of the hexagonal Sb2Te3.38 The diffraction signals of (110) and (015) crystalline planes of Sb2Te3 can be found in the SAED result (Figure 1f). The image (Figure 1g) and the relevant element mapping results (Figure 1h-j) demonstrate that Sb and Te are uniformly distributed in the plate, while the element C is evenly distributed over the entire plate. The crystallographic property is studied by XRD (Figure 2a), where all the diffraction peaks can be indexed to hexagonal Sb2Te3 (JCPDS No.71-0393). Raman spectrum in Figure 2b clearly indicates the presence of carbon in the material, with two strong peaks of 1320 and 1590 cm−1 (D, G band), corresponding to the characteristic of defect-induced mode and graphite mode, respectively.27 On the other hand, the peaks between 50 and 200 cm−1 declare the existence of Sb2Te3.39 The carbon content in the Sb2Te3@C nanoplates can be readily calculated to be 44.9 wt% from the TGA result 6


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(Figure S4a). As shown in Figure S4b, Brunauer-Emmett-Teller surface areas of Sb2Te3 and Sb2Te3@C were determined to be 19.8 and 111.7 m2/g, respectively. The diameter of the pores for Sb2Te3@C is in the range of 3-6 nm (Figure S4c). The chemical composition of Sb2Te3@C was investigated using X-ray photoelectron spectroscopy. As shown in Figure S5a, main peaks including C 1s, Sb 3d, and Te 3d can be observed. Two peaks at 539.4 and 530.1 eV can be related to Sb 3d3/2 and Sb 3d5/2 of Sb3+, respectively (Figure 2c).40 Meanwhile, two small peaks at 538.3 and 532.0 eV can be ascribed to the surface oxidation of the Sb2Te3@C nanocomposite. And the peaks at 584.2 and 573.8 eV can be attributed to Te 3d3/2 and Te 3d5/2 of Te2−, respectively (Figure 2d). In addition, the peaks at 586.4 and 576.0 eV can be related to the presence of TeO2.41 The electrochemical characteristic of Sb2Te3@C was first investigated using CV. As shown in Figure 3a, two peaks at 1.25 and 0.82 V and other small peaks can be observed in the first cathodic scan. In subsequent cycles, two pairs of oxidation/reduction peaks at 1.69 /1.38 V and 1.21 /0.87 V emerged and remained stable. According to previous reports,13 the reaction mechanism of Sb2Te3 electrode during lithiation/delithiation can be described as follows: During discharging: Sb2Te3 → Li2Te + Sb → Li2Te + Li3Sb

(1)

During charging:

(2)

Li2Te + Li3Sb → Li2Te + Sb → Sb2Te3

The peak at 1.25 V in the first scan can be interpreted as the formation of Li2Te during the lithiation of tellurium, and the other small peaks after 0.82 V can be interpreted as the lithiation of antimony.40, 42-44 The two pairs of redox peaks, localized 7



at 0.87 /1.21 V and 1.38 /1.69 V, can be assigned to the lithiation of Sb and Te, respectively.18,

43,

45-46

The obvious potential plateaus presented in the

discharging/charging curves again confirm the reaction is reversible. The initial discharging/charging capacities of Sb2Te3@C were 1590 and 1006 mAh g−1, respectively, with an initial coulombic efficiency of 63.3% (Figure 3b). The low coulombic efficiency is possibly related to the irreversible capacity caused by the formation of SEI on electrode. The cycling performances of the two samples are shown in Figure 3c-d. Specifically, Sb2Te3@C shows a capacity of around 835 mAh g−1 after 200 cycles. On the contrary, the capacity of Sb2Te3 is 650 mAh g−1, and drops quickly to 450 mAh g−1 after 200 cycles. The tap densities of Sb2Te3, Sb2Te3@C, and commercial carbon (BTR New Energy Material Ltd) are determined to be 1.34, 0.86, and 0.50 g cm−3, respectively (Figure S5b). The volumetric capacities of the two samples are shown in Figure 3d. After 200 cycles, Sb2Te3@C demonstrates a stable capacity of 718 mAh cm−3, which is greater than that of Sb2Te3 (650 mAh cm−3). Benefitted from the advantageous structures, Sb2Te3@C possesses excellent cycling response to varying current densities. For Sb2Te3@C, the capacity of 550 mAh g−1 can still be retained, even cycled at 1 A g−1 (Figure 3e). After cycling at 3 A g−1, a capacity of about 720 mAh g−1 can be retained when current density returned to 100 mA g−1. For Sb2Te3, the capacity is decreased as the current density increases, down to 150 mAh g−1 at 1 A g−1. The rate capabilities of the two samples based on volumetric capacities are shown in Figure 3f. Significantly, the Sb2Te3@C nanoplates show long-term cycling

8


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performance at a high current density. As shown in Figure 3g, a capacity of 790 mAh g−1 can be obtained after 500 cycles. To understand the electrochemical property of Sb2Te3@C, further research based on CV was carried out. Figure 4a presents the CV results of the Sb2Te3@C electrode cycled at different sweep rates from 0.1 to 1 mV s−1, with similar broad peaks for all the cycles. The current (i) and sweep rates (v) comply with the following the equation (3):47-48 i = avb

(3)

where a and b represent the adjustable values. Specifically, when b is closed to 1, the electrochemical process is controlled by a capacitive process, while b approaches to 0.5, a diffusion-controlled process dominates. The b-values of the peaks are 0.93, 0.79, 0.92, 0.78, and 0.89 (Figure 4b), respectively, indicative of capacitance-controlled process. To further evaluate the capacitance-controlled capacity and diffusion-controlled capacity, we calculate the contribution from the capacitive process by equation (4),49 i (V) = k1v + k2v1/2

(4)

where k1v and k2v1/2 indicate the contributions from capacitance-controlled and diffusion-controlled process, respectively. The current response (i) at a fixed potential can be determined by k1v and k2v1/2. The result in Figure 4c clearly displays that the capacitance-controlled contributions are 66.7%, 70.8%, 74.6%, and 78.2% at different scan rates, respectively. When it increases to 1 mV/s, the contribution of capacitive process is 83.2% (Figure 4d). 9



Additionally, the as-prepared Sb2Te3@C nanoplates show good Na-ion storage performance, as shown in Figure S6a. Sb2Te3@C delivers a reversible capacity of 573 mAh g−1 at 100 mA g−1 and an initial coulombic efficiency of 52.8%. Also, Sb2Te3@C demonstrates better capacity retention than Sb2Te3, as shown in Figure S6b-c. Also, the Sb2Te3@C nanoplates deliver better rate capability than Sb2Te3 at various current rates (Figure S6d-e). Figure S6f displays the cycling performance of the two samples evaluated at 200 mAh g−1. After 100 cycles, Sb2Te3@C can retain a high capacity of 363 mAh g−1, while Sb2Te3 only delivered 38 mAh g−1. By comparison, the capacity of the Sb2Te3@C nanoplates is greater than those of most reported metal chalcogenidesbased materials for Na/Li storage (Table S1). To analysis the electrochemistry mechanism, CV measurements at different sweep rates were studied. As presented in Figure S7, the contributions from capacitancecontrolled processes are 56.25%, 60.26%, 67.74%, 76.8%, 82.09%, and 83.94% at different scan rates of 0.075, 0.1, 0.3, 0.5, 0.8, and 1 mV/s, respectively. To demonstrate the superior cycling stability of Sb2Te3@C, the structures and morphologies of the Sb2Te3@C and Sb2Te3 electrodes at different discharged/charged states were characterized by ex-situ SEM/TEM. Compared to the pristine states, the structure of cycled Sb2Te3@C shows no obvious changes after 50 cycles for LIBs (Figure 5a-d). On the contrary, Sb2Te3 nanoplates were pulverized into porous structure and small particles after 50 cycles for LIBs (Figure 5e-h). This phenomenon can be ascribed to the protection of carbon shell, helping to buffer volume changes during cycling. Also, the carbon shell prevents the agglomeration and fracturing of the 2D 10


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structure, thus maintaining the stability of SEI, as illustrated in Figure 5i. The EIS results further demonstrated the contribution of carbon shell in preventing the fracturing and reformation of SEI, and improving charge transfer in the Sb2Te3@C electrode. In the EIS spectra (Figure S8), the semicircles, representing the charge transfer resistance (Rct), demonstrates the enhanced charge transfer in Sb2Te3@C. The fitting results (Table S2) based on the equivalent circuit model (Figure S9) demonstrate that the Rct of Sb2Te3@C is much lower than that of Sb2Te3. The EIS data and the high coulombic efficiency of Sb2Te3@C work together to strongly prove the structural stability of Sb2Te3@C during cycling. CONCLUSIONS A novel porous Sb2Te3@C core-shell nanoplates with high tap density has been successfully prepared by a hydrothermal and carbonization technique. In this material, porous Sb2Te3 nanoplates are uniformly encapsulated within a carbon shell. When evaluated as anode for batteries, the material demonstrates excellent high-rate capability and long cycling lifespan. Sb2Te3@C shows a high capacity of 835 mAh g−1 after 200 cycles at a current density of 100 mA g−1 for LIBs, and can retain a reversible capacity of 404 mAh g−1 for SIBs with a remarkable cycling stability. Electrochemical dynamic analysis suggests the dominance of the capacitive-controlled mechanism for alkali metal ion storage in the Sb2Te3@C electrode. The good electrochemical performance demonstrates a great potential of Sb2Te3@C as an anode material for nextgeneration battery systems. ASSOCIATED CONTENT 11



Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: XX.XXXX/acsami.XXXXXXX. Schematic illustration of the synthesis process; SEM and TEM images of the Sb2Te3 nanoplates; SEM, TEM and HR-TEM images of Sb2Te3@RF; TGA curves, nitrogen sorption isotherms; XPS survey spectrum; electrochemical performance for SIBs; CV curves and corresponding linear fits of the Sb2Te3@C electrode for SIBs; EIS spectra and the fitting values of resistance for the electrodes (PDF) AUTHOR INFORMATION Corresponding Authors: *E-mail: [email protected] (C. L. Z.) *E-mail: [email protected] (C.F. Z.) ORCID Chaofeng Zhang: 0000-0001-6188-6886 Sen Xin: 0000-0002-0546-0626

Author Contributions This manuscript was written through contributions from all authors. All authors have given approval to the final version of the manuscript. W.Z and Q.Z. contributed equally.

Notes The authors declare no competing financial interest. ACKNOWLEDGMENTS This work was supported by National Natural Science Foundation of China (NSFC 12


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FIGURES AND CAPTURES

Figure 1. SEM (a) and TEM (b) images of the Sb2Te3@C sample. (c-e) HRTEM images of the Sb2Te3@C sample. (f) The corresponding SAED pattern of the sample. TEM image (g) of Sb2Te3@C and corresponding elemental mapping results (h, I, j) for the distribution of Te, Sb, and C, respectively.

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Figure 2. (a) XRD patterns of Sb2Te3 and Sb2Te3@C. (b) Raman spectra of the Sb2Te3 and Sb2Te3@C. (c) Sb 3d core-level spectrum of the as-synthesized Sb2Te3@C sample. (d) Te 3d core-level spectrum of the as-synthesized Sb2Te3@C sample.

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Figure 3. (a) CV curves of Sb2Te3@C for LIBs at a scan rate of 0.01 mV s-1. (b) Chargedischarge voltage profiles of Sb2Te3@C electrode. (c) Gravimetric capacities and (d) volumetric capacities vs. cycling number of Sb2Te3@C and Sb2Te3 electrodes at a current density of 100 mA g−1. (e) Gravimetric capacities and (f) volumetric capacities of the Sb2Te3@C and Sb2Te3 electrodes at different current densities. (g) Long-term cycling performance of Sb2Te3@C electrodes tested at a current density of 500 mA g−1.

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Figure 4. (a) CV curves of one Sb2Te3@C electrode for LIBs at various scan rates (0.1-1 mV s−1) after first cycle. (b) Linear plots of log (i) vs. log (v), where i is the peak current and v is the scan rate. (c) Contribution ratios of diffusion-controlled and capacitive capacities at different scan rates (0.1, 0.2, 0.3, 0.5 and 1 mV s−1). (d) The CV curve of Sb2Te3@C at a scan rate of 1 mV s−1, the shaded area represents the capacitive contribution.

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Figure 5. SEM (a) and TEM (b) images of the fully discharged Sb2Te3@C electrode after 50 cycles at a current density of 100 mA g−1 for LIBs. SEM (c) and TEM (d) images of the fully charged Sb2Te3@C electrode after 50 cycles at a current density of 100 mA g−1 for LIBs. SEM (e) and TEM (f) images of the fully discharged Sb2Te3 electrode after 50 cycles at a current density of 100 mA g−1 for LIBs. SEM (g) and TEM (h) images of the fully charged Sb2Te3 electrode after 50 cycles at a current density of 100 mA g−1 for LIBs. (i) Schematic illustration of the cycling process for Sb2Te3@C and Sb2Te3 electrodes.

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TOC Figure

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Facile Synthesis of Carbon-Coated Porous Sb2Te3 Nanoplates with

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