ZnS-Sb2S3@C Core-Double Shell Polyhedron Structure Derived from Metal−Organic Framework as Anodes for High Performance Sodium Ion Batteries Shihua Dong, Caixia Li, Xiaoli Ge, Zhaoqiang Li, Xianguang Miao, and Longwei Yin* Key Laboratory for Liquid−Solid Structural Evolution and Processing of Materials, Ministry of Education, School of Materials Science and Engineering, Shandong University, Jinan 250061, PR China S Supporting Information *
ABSTRACT: Taking advantage of zeolitic imidazolate framework (ZIF-8), ZnS-Sb2S3@C core-double shell polyhedron structure is synthesized through a sulfurization reaction between Zn2+ dissociated from ZIF-8 and S2− from thioacetamide (TAA), and subsequently a metal cation exchange process between Zn2+ and Sb3+, in which carbon layer is introduced from polymeric resorcinol-formaldehyde to prevent the collapse of the polyhedron. The polyhedron composite with a ZnS inner-core and Sb2S3/C double-shell as anode for sodium ion batteries (SIBs) shows us a significantly improved electrochemical performance with stable cycle stability, high Coulombic efficiency and specific capacity. Peculiarly, introducing a carbon shell not only acts as an important protective layer to form a rigid construction and accommodate the volume changes, but also improves the electronic conductivity to optimize the stable cycle performance and the excellent rate property. The architecture composed of ZnS inner core and a complex Sb2S3/C shell not only facilitates the facile electrolyte infiltration to reduce the Na-ion diffusion length to improve the electrochemical reaction kinetics, but also prevents the structure pulverization caused by Na-ion insertion/extraction. This approach to prepare metal sulfides based on MOFs can be further extended to design other nanostructured systems for high performance energy storage devices. KEYWORDS: ZIF, core-double shell, metal sulfide, carbon layer, sodium ion battery
S
such as Sn-based and Sb-based sodium anode material with a theoretical capacity of 847 mAh g −1 (Na15Sn4) and 660 mAh g −1 (Na3Sb), respectively.13,14 Recently, metals chalcogenide (MxSy, M = Co, Zn, Ni, Mo, Sb, Fe, etc.) have been reported as SIBs anodes.15 For example, ZnS, as a new nontoxic and low cost SIBs anode,16,17 shows a stable cycle performance. Antimony sulfide, can accommodate 12 mol of Na ions per mole, can display larger theoretical capacity (947 mAh g −1) than Sb, and possesses a better electrical conductivity than Sboxide.18−21 Several kinds of antimony sulfide structured SIBs anodes, such as the flower-like Sb2S3,11 Sb2S3 nanorods22 and amorphous Sb2S3 nanoparticles,23−25 are reported. Coupling sulfides with carbon materials is effective to improve inferior electrode electron conductivity of metal sulfides as SIBs and alleviate the volume changes from the charge/discharge
odium ion batteries (SIBs) have attracted more attention due to their most important advantages such as the low cost, abundant natural resources and the suit oxidation reduction potential (−2.71 vs SHE).1−4 The similar energy storage mechanism to lithium ion batteries (LIBs) and abovedescribed advantages, make SIBs as an alternative for LIBs for the potential large-scale application of portable devices and electric vehicles.5−7 However, the inferior electrochemical performance and the severe structure pulverization upon sodiation/desodiation resulted from the reduced electrochemical reaction kinetics and the unstable solid electrolyte interphase (SEI) layer caused by the larger ion size of Na ion (∼1.09 Å), 55% larger than that of Li+, need to be resolved urgently. Therefore, the critical point to develop high performance SIBs lies in the rational design on microstructure of the anode materials to realize the ideal Na-ion insertion/ extraction and alleviate the strain and stress from the volume changes during charge/discharge process.8−11 Among the SIBs anode materials, Na alloy-based electrodes display higher gravimetric and volumetric specific capacities,12 © 2017 American Chemical Society
Received: May 12, 2017 Accepted: June 7, 2017 Published: June 7, 2017 6474
DOI: 10.1021/acsnano.7b03321 ACS Nano 2017, 11, 6474−6482
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ACS Nano process, thus to improve the charge transfer kinetics and electrochemical performance.26,27 Recently, zeolitic imidazolate framework (ZIF), a class of metal organic frameworks (MOFs) composited of metal ions/ clusters and organic ligands,28,29 has been broadly proven to be a significant candidate in photocatalysis field, solar energy, solid oxide fuel cell and secondary battery.30−32 Owing to the superiority of controllable structures, huge surface area, superb electronic conductivity, tunable pore size and high porosity,33−35 it has been used as an important alternative precursor to fabricate the porous metal/carbon hybrid anode materials, which are beneficial to the electrochemical reaction kinetics, the buffer of volume changes and further the electrochemical property.36,37 Recently, Lou’s group synthesized CoS2 nanobubble, double-shelled Co(OH)2/LDH nanocages and CoSe@ carbon nanoboxes transformed from cobalt acetate hydroxide solid precursors (ZIF-67) for the secondary energy battery, demonstrating a uniform morphology and superb electrochemical performance.38−40 While core−shell structure RGO@ CoP@FeP with abundant pores stemmed from Co(OH)2@PB precursor is reported through a well-designed strategy, revealing a higher capacity of 456.2 mAh g −1 at 200th cycle.37 For Sb2S3, one mole of Sb2S3 can get 12 mol of electrons and Na-ion, while for ZnS, one mole of ZnS can get 2.2 mol of electrons and Na-ion, it is of great importance and challenge to take both advantages of Sb2S3 and ZnS to design sulfide composites for SIBs anodes with high rate capability and long-term cycling stability. Herein, capitalizing on full advantages of the zeolitic imidazolate framework (ZIF-8), a type of the core-double shell structure zinc sulfide-antimony sulfide@carbon (ZnSSb2S3@C) sodium anode electrode is rationally designed through a sulfidation reaction with thioacetamide (TAA) and a cation exchange process by introducing the protective RF layer. The composite with a ZnS inner-core and the Sb2S3/C double-shell shows us a stable structure to undertake the volume and strain changes during the repeated Na+ insertion/ extraction processes. In addition, the charge transfer kinetics and the electronic conductivity can be improved due to the carbon outer shell, which contributes immensely to the remarkable electrochemical performances.
Scheme 1. Synthesis Process of ZnS-Sb2S3@C Core-Double Shell Polyhedron Composite
cation exchange route between Zn2+ and Sb3+ (3ZnS + 2SbCl3 → Sb2S3 + 3ZnCl2) is adopted (Figure S1),43 the Sb2S3 particles can be established to further develop an analogous inner shell which attaches to the RF outer shell.45,46 Meanwhile, ZnS self-assembled core forms from fractional ZnS nanoparticles. Herein, RF layer plays a role of protector and template to guarantee the structural stability of the polyhedron structure and morphology. And it provides pore canal to allow the ions transition to realize the chemical reactions. The C layer from RF layer not only facilitates the facile electrolyte infiltration to reduce the Na-ion diffusion length to improve the electrochemical reaction kinetics, but also prevents the structure pulverization caused by Na-ion insertion/extraction, alleviates the volume changes and stress. Therefore, when ZnSSb2S3@C is used as anodes for sodium ion batteries (SIBs), it is expected to possess good electrochemical performance and structure stability. As depicted in Figure 1, the uniform dispersed ZnS@RF polyhedrons show an average size of 1.5 μm, larger than 1.2 μm of the ZIF-8 template. Due to protection and restriction of RF layer with a thickness of about 30 nm, the solid polyhedron changes to regular hollow ZnS@RF polyhedron through a sulfurization process (Figure S2,3), in which the hollow ZnS@ RF consists of ZnS inner shell with scattered tiny ZnS particles, and the RF as an outer shell. Meanwhile, the uniform polyhedron morphology with a size and morphology dispersity can be maintained superbly due to the introduced RF shell (Figure 1a−d). In addition, the component of ZnS can be confirmed by HRTEM lattice image and electron diffraction (ED) pattern in Figure 1e,f. The marked d-spacing of 0.31 nm corresponds well to that of (111) plane of ZnS (PDF. 05− 0566), and the diffraction rings in ED pattern match well with (111), (220) and (330) plane of ZnS, indicating the formation of ZnS nanoparticles from ZIF template. The microstructures of the ZnS-Sb2S3@C core-double shell composite are depicted in Figure 2. On the basis of the uniform hollow ZnS@RF polyhedron, the integrated ZnS-Sb2S3@C polyhedron with an average size of approximate 1.5 μm (Figure 2a) can be obtained via the cation exchange process between Zn2+ and Sb3+, with the polyhedron morphology and size well retained. TEM images in Figure 2b,c show a perfect
RESULTS AND DISCUSSION The ZnS-Sb2S3@C core-double shell composite is depicted in Scheme 1. According to the literature,41 the interior of ZIF-8 nanocrystals is strongly hydrophobic and exterior surfaces are hydrophilic due to the existence of terminal N−H functional groups (in alkaline media). Therefore, making the best of the hydrophilic nature and capacity for H-bonding from ZIF-8, as well as the hydroxyl groups from the polymeric resorcinolformaldehyde (RF), ZIF-8@RF can be obtained, in which the coordination sites stimulate the growth of contiguous RF layer as a three-dimensional network cross-linked on the ZIF-8 surface.41,42 Here, the aim to introduce the RF shell is to stabilize the polyhedron structure and morphology to fabricate the unbroken hollow ZnS@RF polyhedron during the sulfurization process. 29,43,44 Attentively, because of the preferential reaction between Zn2+ dissociated from the ZIF-8 and S2− hydrolyzed from TAA which can pass through the RF polymer, the ZnS particles form primarily between the ZIF-8 and RF shell, final to get hollow ZnS@RF polyhedron until the internal ZIF-8 is consumed absolutely. Subsequently, to prepare the ZnS-Sb2S3@C core-double shell polyhedron, an easy metal 6475
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Figure 1. ZnS@RF polyhedrons. (a,b) SEM images, (c,d) TEM images show a thickness of 30 nm for RF layer shell. (e) HRTEM lattice image of ZnS nanoparticles. (f) Electron diffraction pattern.
Figure 2. ZnS-Sb2S3@C core-double shell polyhedron composite. (a) FE-SEM (b,c) TEM. (d,e) HRTEM lattice image and Electron diffraction pattern of Sb2S3. (f,g) Line scanning curves and elemental mapping images of C, S, Sb, Zn elementals.
zone axis, as depicted in ED pattern in Figure 2d. In addition, the line scanning curves in Figure 2f and elemental mapping images in Figure 2g, suggest the corresponding distribution of C, S, Sb and Zn elements for the ZnS-Sb2S3@C core-double shell structure. Therefore, the ZnS-Sb2S3@C core-double shell structure suggests the feasibility of the design strategy, and stable framework and the sufficient room conducive for Na-ion
homogeneity, dispersity of the core-double shell structure. The ZnS-Sb2S3@C core-double shell composite is composed of ZnS inner core and Sb2S3 inner shell connected on the C outer shell by a self-assembly process. To further reveal the microstructure, the HRTEM lattice image and electron diffraction (ED) pattern are displayed in Figure 2d,e. The marked d-spacing of 0.32 and 0.35 nm corresponds well to that of (0−21) and (1−1−1) plane of Sb2S3 (PDF. 43−1393), which is taken along [312] 6476
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Figure 3. (a) XRD pattern and (b) Raman spectra of ZnS-Sb2S3@C core-double shell polyhedron composites.
Figure 4. ZnS-Sb2S3@C core-double shell composites. (a) XPS survey spectrum, (b−d) High-resolution XPS spectrum of S 2p, Sb 3d, and Zn 2p.
products, confirming the existence of Sb, Zn, C, and S elements in Figure 4a. Primarily, the high resolution XPS spectrum of S 2P depicted in Figure 4b determents the chemical bonding state of S2− at 161.12 and 163.76 eV in the S−Sb/S−Zn bonded structure.20,47,48 Besides, the peak at 164.92 eV suggests a covalently bond to carbon, implying the Sb2S3 inner shell is connected on the C shell.48,49 Additionally, the presence of Sb3+ and Zn2+ can be proved by the peaks located at 539.45 and 530.11 eV for Sb 3d3/2 and Sb 3d5/2 as well as 1025.29 eV for Zn 2p (Figure 4c,d). According to XPS analyses, the mass content of C is 35% and the molar ration for Sb2S3 and ZnS is about 16:1. To investigate the sodium storage mechanism of ZnSSb2S3@C core-double shell composites, the sodiation/desodiation electrochemical reaction process is revealed by cyclic voltammogram (CV) curves in Figure 5a at a scan rate of 0.1 mV s −1 over the voltage range of 1.8−0.01 V. In the first cycle, the potential pair at 0.84/1.28 V for Sb2S3 is attributed to conversion reaction between Sb2S3 and Sb13,18,50 (eq 1), and another reduction/oxidation potential pair at (0.27 and 0.45)/
insertion indicates the potential superior electrochemical performance. X-ray diffraction (XRD) pattern in Figure 3a can be used to further determine the crystal structure of ZnS-Sb2S3@C coredouble shell composites. It is shown that most of the diffraction peaks match well with stibnite structure for Sb2S3 (PDF. 43− 1393). The peaks centered at 28.6°, 47.6°, and 56.3° correspond to (111), (220), and (311) plane of ZnS inner core (PDF. 05−0566). It is indicated that the ZnS-Sb2S3@C core-double shell composites with high crystallinity are successfully fabricated after a sequence of chemical reaction (Figure S4). The Raman spectra of ZnS-Sb2S3@C core-double shell composites are displayed in Figure 3b. The bands at 281 cm −1 and 309 cm−1 can be attributed to the symmetric vibrations of Sb2S3 pyramidal units with C3v symmetry, and the peak at 350 cm−1 can be assigned to the presence of ZnS.24 While the bands at 1345 cm −1 and 1580 cm −1 are associated with D-band and G-band of carbon materials.20 XPS spectra are used to characterize the elemental composition component and chemical bonding state of the 6477
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Figure 5. (a) CV curves at a scan rate of 0.1 mV s −1 in the voltage range of 1.8−0.01 V. (b) Representative galvanostatic charge/discharge curves at a current density of 100 mA g −1. (c,d) XRD patterns of the ZnS-Sb2S3@C core−shell electrode at different discharge−charge stages.
The peak at 1.00 V corresponds to electrolyte decomposition and the intercalation of Na+ into the Sb2S3 and ZnS structure. Other new peaks around 0.60 and 0.30 V are associated with the conversion reaction (eq 1) and the alloy reaction for Sb2S3 (eq 2). During the anodic scan, there are three peaks located around 0.74, 0.95, and 1.25 V, which can be attributed to the formation of Sb and Zn (eq 2, 4), ZnS (eq 3), and Sb2S3 (eq 1) respectively.21 Figure 5b shows the galvanostatic discharge−charge profiles of the ZnS-Sb2S3@C core-double shell composites at a current of 100 mA g −1 over 1.8−0.01 V. In accordance with the CV curves, the obvious platforms around 1.0−0.2 V during the following sodiation process can be observed, corresponding to the conversion reaction of sulfide with Na and the alloying reaction of Sb/Zn with Na.51,52 Therefore, on the basis of the special sodium storage mechanism of ZnS and Sb2S3, as well as the stable core-double shell structure, the high initial discharge and charge capacity of 1675 and 1029 mAh g −1 with an initial Coulombic efficiency of 61.4% can be obtained, predicting the excellent electrochemical performance. To further verify the above special electrochemical reaction, the XRD patterns for intermediate products at different discharge−charge stages are shown in Figure 5c,d. Compared to the fresh anode, several weak diffraction peaks related to Sb2S3 weaken at 0.84 V and even disappear at 0.45 V during the reduction reaction, implying that the Sb2S3 has decomposed gradually and metal Sb is formed (eq 1). In addition, the products of Sb (51.6°, PDF 35−0732) and Na3Sb (18.64°, PDF 65−3523) are remained from 0.45 to 0.27 V, confirming the multistep alloying transformation of Sb−Na (eq 2), which is in accordance with the analyses in CV curves. When discharged at 0.01 V, more characteristics peaks located at 33.38° and 39.91° corresponding to (110) and (201) planes of Na3Sb, and a peak at 41.55° related to NaZn13 are observed, suggesting the alloying process of Na-ion insertion into Sb2S3/ZnS finishes.
0.74 V is in accordance with the multistep alloying/dealloying transformation between Sb and Na3Sb (eq 2).13,22,50 Moreover, for ZnS, two potential pairs at 0.5/0.95 V and 0.17/0.7 V are mainly due to the reversible Na-ion insertion/extraction process to form Zn (PDF 04−0831, eq 3) and NaZn13 (PDF 65−6561, eq 4), respectively (Figure S5).16,29,51 Therefore, based on the above reaction mechanism, one mole of Sb2S3 can get 12 mol of electrons and Na-ion, and one mole of ZnS can get 2.2 mol of electrons and Na-ion, revealing a high specific capacity for the ZnS-Sb2S3@C SIB anode. The related electrochemical reaction can be described as following equations: Conversion reaction: Sb2 S3 + 6Na + + 6e− ↔ 2Sb + 3Na 2S
(1)
Alloying/dealloying reaction: 2Sb + 6Na + + 6e− ↔ 2Na3Sb
(2)
Conversion reaction: ZnS + 2Na + + 2e− ↔ Zn + Na 2S
(3)
Alloying/dealloying reaction: 13Zn + 3Na + + 3e− ↔ 3NaZn13
(4)
For the CV curves of ZnS@C, in the first cathodic scanning process, one broad peak around 1.0 V is mainly contributed to the first sodium-ion insertion and the formation of solid electrolyte interphase (SEI) layer due to the decomposition of electrolyte, while in the first anodic scanning, the anodic peaks at 0.74 and 0.95 V are related to the dealloying reaction (eq 4) and conversion reaction (eq 3).16 For the CV curves of ZnS-Sb2S3@C core-double shell polyhedron anode, in the first cathodic scan, three strong current peaks are present, locating at 1.00, 0.60, and 0.30 V. 6478
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Figure 6. (a) Cycling performance and (b) Rate capability at a current density of 100 mA g
Notably, Na2S phase cannot be observed due to its amorphous feature. On the contrary, when the electrode is charged from 0.74 to 1.28 V, the dealloying reaction (eq 2: 2Na3Sb→ 2Sb + 6Na+ + 6e−) and the formation of Sb2S3 (eq 1: 2Sb + 3Na2S → Sb2S3 + 6Na+ + 6e−) can be proved by the phase evolution of Na3Sb, Sb and Sb2S3 in Figure 5d. Upon 1.8 V, the intermediate products disappear completely, and only ZnS and Sb2S3 can be found, implying the important phase evolution upon desodiation process. As expected, the ZnS-Sb2S3@C core-double shell composite electrode exhibits superb cycling stability at a current rate of 100 mA g −1, as shown in Figure 6a. During the first several cycles, the capacity of the ZnS-Sb2S3@C composite electrode decreases monotonically, which might be ascribed to the SEI film stabilization and irreversible trapping of some sodium in the lattice of sulfide.40 In addition, according to the reference,25 the nonconducting NaxS phase also might contribute to the gradual capacity decay. After 20 cycles, the specific capacity tends to be stable, showing good cycle stability. It is noted that the core-double shell composite electrode still demonstrates the high reversible capacity of 630 mAh g −1 after 120 cycles with the high Coulombic efficiency (CE) around almost 100% over the course. In comparison with capacity and cycle stability of the ZnS@C hollow polyhedron anode (Figure S6), the electrochemical performance of the ZnS-Sb2S3@C SIBs anode is significantly enhanced. And that excellent electrochemical performance of ZnS-Sb2S3@C SIBs anode can be comparable and superior to that of the previously reported SIBs based on Sb2S3 anodes (Table 1), which can be assigned to the cooperative contribution of components and the stable structure with sufficient space to immensely accommodate the volume expansion during the repeated Na-ion insertion/ extraction. After 50 cycles, the structure and morphology of the 50 cycled anodes are shown in Figure S7−S8. In accordance with the analyses in Figure 5, the integrated core-double shell polyhedron with a diameter of 1.5 μm can be maintained superbly with the protection and restriction of carbon shell. The presence of Na3Sb/NaZn13 suggests and confirms the electrochemical reaction mechanism, indicating a high specific capacity of the ZnS-Sb2S3@C SIBs anode. The architecture composed of ZnS inner core and a complex Sb2S3/C shell not only facilitates the facile electrolyte infiltration to reduce the Na-ion diffusion length to improve the electrochemical reaction kinetics, but also alleviates the successive volume expansion and prevents the structure pulverization caused by Na-ion insertion/extraction (Figure S7e). Therefore, the superb
−1
of ZnS-Sb2S3@C core−shell SIBs anodes.
Table 1. Comparison of Electrochemical Performance between the Present Work and Previously Reported Sb2S3Based Anodes for SIBs anode materials rGO/Sb2S3 rGO/Sb2S3 rgo/Sb2S3 Sb2S3@MWCNT MWCNT@Sb2S3@ PPY Sb2S3 Sb2S3 Sb2S3 Sb2S3/P/C Rod-Like Sb2S3@C ZnS This work
current density (mA g−1)
cycle number (cycles)
reversible capacity (mAh g −1)
reference
50 100 50 50 100
50 60 50 50 80
670 306 581 412 500
13 18 19 20 21
100 50 50 50 100 100 100
100 100 50 100 100 50 120
570 512 853 611 691 481 630
22 23 24 27 52 16
electrochemical performance of the ZnS-Sb2S3@C core-double shell composites electrode has been obtained as expected. Combing the results of CV curves in Figure 5a, XRD patterns of the ZnS-Sb2S 3@C core−shell electrode at different discharge−charge stages (Figure 5c,d), and the TEM images of ZnS-Sb2S3@C core-double shell composite SIBs anodes after 50 cycles, it clearly provides the direct evidence for the electrochemical reaction mechanism of the ZnS-Sb2S3@C core−shell SIBs anode. The electrochemical reaction mechanism for the ZnS-Sb2S3@C core−shell SIBs anode can be well described as reactions of eq 1 to eq 4. The rate performance of the ZnS-Sb2S3@C composite electrode is shown in Figure 6b. A specific capacity of 1043, 683.0, 525.6, and 390.6 mAh g −1 can be obtained at the current density of 100, 200, 400, and 800 mA g −1, respectively. When the current density returns back to 100 mA g −1, it can recover back to 661.9 mAh g −1 after 50 cycles. That superior specific capacity, cycle stability and rate performance of ZnS-Sb2S3@C core-double shell composites can be revealed from the electrochemical impedance spectroscopy (EIS) in Figure S9. In contrast with the fresh electrode, the diameter of the semicircle after 3th cycle decreases, indicating the enhanced charge transfer kinetics and intensive electronic conductivity. Therefore, together with the special stable core-double shell structure with enough space, the excellent electrochemical performance has been testified by the fast transfer of Na-ions and electrons. 6479
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CONCLUSIONS In summary, we report a ZnS-Sb2S3@C core-double shell polyhedron based on the ZIF-8 template to be used as sodium anode electrode. With the protection of the carbon outer shell, the sulfidation reaction and cation exchange process to obtain ZnS inner core and Sb2S3 inner shell have been executed successfully. Benefiting from the structural and compositional features, the ZnS-Sb2S3@C core-double shell composites show excellent sodium storage performance with a high reversible capacity of 630 mAh g −1 at a current density of 100 mA g −1 after 120 cycles, indicating the promising application for high performance energy storage devices.
AUTHOR INFORMATION Corresponding Author
*Tel.: + 86 531 88396970. Fax: + 86 531 88396970. E-mail:
[email protected]. ORCID
Longwei Yin: 0000-0003-3768-6846 Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS We acknowledge support from the project supported by the Sate Key Program of National Natural Science of China (No.: 51532005), National Nature Science Foundation of China (No.: 51472148, 51272137), the Tai Shan Scholar Foundation of Shandong Province.
EXPERIMENTAL SECTION Syntheses of ZIF-8@RF. ZIF-8 is first synthesized by a mixed solution composed of 2.38 g Zinc nitrate hexahydrate, 1.31 g 2Methylimidazole and 200 mL methanol with 11 h aging at room temperature. Then ZIF-8@resorcinol-formaldehyde (ZIF-8@RF) can be fabricated according to the reference41 with a modified version: 0.2 g ZIF-8, 14 mL deionized water and 6 mL ethanol are mixed and stirred ceaselessly at room temperature. Thirty minutes later, 0.23 g Hexadecyl trimethyl ammonium Bromide (CTAB), 0.035 g resorcinol and 0.1 mL Ammonium Hydroxide are added. Another 30 minutes later, 0.06 mL formaldehyde solution is added again. Eight hours later, the pink ZIF-8@resorcinol-formaldehyde (ZIF-8@RF) layer can be given by washed with deionized water. Syntheses of ZnS@RF and ZnS-Sb2S3@C. After a microthermal solvothermal sulfidation process, in which 100 mL ethanol solution mixed with 0.1 g ZIF-8@RF and 0.3 g Thioacetamide (TAA) is transferred into a Teflon-lined stainless-steel autoclave and heated at 85 °C for 8 h, ZnS@RF is obtained. Then, ZnS-Sb2S3@C core-double shell structure is fabricated successfully as follows: 0.1 g ZnS@RF and 0.4 g Antimony trichloride are dissolved in 400 mL ethanol at 60 °C for 20 h; then the obtained product is annealed under argon at 530 °C for 2 h with 3 °C/min rate. Materials Characterization. The structure and chemical components of the products are characterized by X-ray diffraction (XRD) (Rigaku D/Max-KA diffractometer with Cu Kα radiation (λ = 1.5406 Å)), X-ray photoelectron spectroscopy (XPS, ESCALAB 250 with 150 W Al Ka probe beam) and Raman spectroscopy (JY HR800). The morphology of the synthesized products is analyzed by fieldemission scanning electron microscopy (FE-SEMSU-70) and highresolution transmission electron microscopy (HR-TEM, Tecnai 20UTwin) attached X-ray energy dispersive spectrometry (EDS). Electrochemical Measurements. To test the electrochemical performance, glass fiber from Whatman is adopted, the active materials are first mixed with acetylene black and binder (LA-132) in a weight ratio of 70:20:10 in water to be spread onto Cu foil substrate and be used as the working electrode, a sodium metal is used as reference electrode, and a solution of 1.0 M NaClO4 in PC = 100 Vol% with 5.0% FEC is used as the electrolyte. Fresh coin cells (2025 coin-type) are assembled in an Ar-glovebox. Charging/discharging tests are performed in potential range of 0.01−1.8 V on a LAND CT2001A batterytest system (Wuhan, China) at room temperature. The cyclic voltammetry (CV) curves and impedance spectroscopy measurements can be obtained at an electrochemical workstation (PARSTAT2273) between 0.01 and 1.8 V at a scan rate of 0.1 mV s −1.
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ASSOCIATED CONTENT S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.7b03321. Additional characterization data, additional electrochemical data and sodium storage mechanism (PDF) 6480
DOI: 10.1021/acsnano.7b03321 ACS Nano 2017, 11, 6474−6482
Article
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