N, S Co-Doped Carbon Composite from Zn

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Facile Synthesis of ZnS/N, S Co-Doped Carbon Composite from Zn Metal Complex for High-Performance Sodium-Ion Batteries Mingjun Jing, Zhengu Chen, Zhi Li, Fangyi Li, Mengjie Chen, Minjie Zhou, Binhong He, Liang Chen, Zhaohui Hou, and Xiaobo Chen ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b15659 • Publication Date (Web): 15 Dec 2017 Downloaded from http://pubs.acs.org on December 17, 2017

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ACS Applied Materials & Interfaces

Facile Synthesis of ZnS/N, S Co-Doped Carbon Composite from Zn Metal Complex for HighPerformance Sodium-Ion Batteries Mingjun Jing,a Zhengu Chen,a Zhi Li, a Fangyi Li,a Mengjie Chen,a Minjie Zhou,a Binhong He,a Liang Chen,a Zhaohui Hou*a and Xiaobo Chen*b a

College of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology,

Yueyang 414006, China. b

Department of Chemistry, University of Missouri – Kansas City, Kansas City, Missouri, 64110,

USA.

KEYWORDS: ZnS/carbon composite, N, S co–doped, zinc pyrithione, bridges, sodium–ion batteries

ACS Paragon Plus Environment

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ABSTRACT: ZnS coated on N, S co–doped carbon (ZnS/NSC) composite has been prepared utilizing zinc pyrithione (C10H8N2O2S2Zn) as raw material via calcination. Through activation using Na2CO3 salt, ZnS nanoparticles encapsulated in NSC (denoted as A–ZnS/NSC) with mixed–crystal structure has also been obtained, which reveals much larger specific surface area and more bridges between ZnS and NSC. Based on the existence of bridges (C–S–Zn and S–O– Zn bonds) and the modification of carbon from N, S co–doping, the A–ZnS/NSC composite as an anode for sodium–ion batteries (SIBs) displays significantly enhanced electrochemical performances with a high reversible specific capacity of 516.6 mA h g – 1 (at 100 mA g–1), outstanding cycling stability (96.9% capacity retention after 100 cycles at 100 mA g–1), and high rate behavior (364.9 mA h g–1 even at 800 mA g–1).


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1. INTRODUCTION Sodium–ion batteries (SIBs) have attracted considerable attention as one of the most promising candidates for electrical–energy–storage, owing to the high abundant sodium element from cheap sources and decent energy densities.1-2 Recently, metal sulfides (including layered and nonlayered) with high theoretical specific capacity display greater performance over other anode materials for SIBs.3 Non–layered metal sulfides (such as FeS2, CoS2, NiS2, CuS, ZnS, MnS and so on) are very popular because of their low price, compared with layered metal sulfides (for example, MoS2, WS2, SnS2, etc.).3-5 Particularly, non–toxic ZnS as anode exhibits high initial Coulombic efficiency (above 70%, vs. about 40 % of carbon material), which is popularizing and drawing more attention for SIBs.6 The proposed sodiation/desodiation mechanism of ZnS includes conversion reaction: ZnS+2Na + 2e–↔Na2S+Zn and alloying/dealloying reaction: 13Zn + Na+ + e– ↔ NaZn13.7-8 During the Na+ insertion/extraction processes, there is a large volume expansion in ZnS electrode, which becomes one of the bottlenecks in the development of ZnS for SIB applications. Compared to the Li–ion batteries (LIBs), the volume change in SIBs is more severe because of the large ionic radius 1.02 Å of Na+ (about 55% larger than that of Li+).9-10 Another problem of the ZnS anode material is its poor electrical conductivity.11 Due to these drawbacks, pure ZnS always suffers from poor rate and cycling stability. Based on studies about some similar materials,2, 6, 12-17 the following strategies are used to solve these problems: (i) utilizing other electrolytes (such as organic liquid, ether–based electrolytes, and so on) to improve the rate of ion diffusion and electrochemical reversibility, (ii) designing unique morphologic structures to remit volume expansion, (iii) constructing composite with high electrical conductivity material, especially various carbon materials. Among these approaches, the third method is regarded as


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one of the most effective ways.18-19 Carbon materials, as a conducting matrix and a mechanical cushion, can enhance the electron transport and buffer the volume change of ZnS particles. For example, ZnS–GO composite prepared via a microwave–assisted method displays a much better capacity retention (88%) than that of pure ZnS nanoparticles (15.6%).8 Doping and co–doping with heteroatom (e.g., N, B, S, P) have been applied to effectively improve the physicochemical properties of carbon.9-10, 20 For example, N doping can improve the electronic conductivities and Na+ storage capacities of various carbon materials due to the introduction of N–doped defects and functionalized groups.21 S–doped carbon can significantly expand the interlayer distance to promote the insertion/extraction of Na+ ions on account of the larger covalent radius of S (102 pm) compared with C (77 pm).22 It is stressing that co–doping may provide more outstanding performances attributed to the synergetic effect.10, 23-24 Therefore, N, S co–doped carbonaceous materials have been applied to construct composite with ZnS, which might be an operative approach to solve the drawbacks of ZnS as an anode for SIBs. Currently, two main synthetic approaches have been utilized to prepare ZnS/Carbon composites. In the first approach, ZnS materials are firstly obtained and then coated with different carbon materials using various carbon precursors such as glucose, polydopamine, etc.7, 25

In the second approach, various kinds of carbon materials (GO, carbon nanotube, etc.) are

added into the system which includes Zn and S sources to grow ZnS.26-27 However, these methods always suffer from tricky multi–step processes and high cost. In addition, preparation of N, S co–doped carbonaceous materials normally needs to introduce extra N and S sources, such as thiourea, 1–allyl–2–thiourea, 2–aminothiophenol, polyrhodanine and so on.28-30 Just think, if the precursors of carbon contained N and S, the preparation process would become simpler. Mullins et al got Sn/NC via a simple clinkering process using SnCl4 mixed with nitrilotriacetic


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acid.9 Based on the above investigations, we design a facial approach to obtain the ZnS/N, S co– doped carbon (ZnS/NSC) composite with utilizing low–cost Zn metal complexes as raw material. In this work, the ZnS/NSC composite has been firstly prepared through direct calcination of Zinc pyrithione (zinc pyridine–2–thiol–N–oxide) that is a common Zn metal complex used for over 50 years in personal hygiene.31 The Zinc pyrithione is served as the single source for both ZnS and NSC. Furthermore, activated ZnS/NSC (A–ZnS/NSC) has been also got via the same process with the addition of Na2CO3 salt. More significantly, the effective chemical bonding between ZnS and NSC can help to enhance cycling stability and rate behavior of as–prepared composite for SIBs. 2. EXPERIMENTAL SECTION 2.1 Synthesis of active materials ZnS/NSC composite was prepared using thermal treatment Zinc pyrithione (zinc pyridine–2– thiol–N–oxide, C10H8N2O2S2Zn, Sigma–Aldrich, ≥ 95%). Zinc pyrithione (2.50 g), a white powder, was calcined under Ar flow at 600 °C for 2 h with the heating rate of 5 °C/min. Then, the freshly as–prepared powder was washed by utilizing distilled water (350 mL) and ethanol (50 mL), and dried at 80 oC for 12 h, to get black ZnS/NSC composite. The heat-treatment temperature (600 oC) has been determined based on the analysis of various products prepared at various temperature (450 oC, 600 oC and 750 oC). Figure S1 illustrates the size of ZnS becomes bigger with rising temperatures. The cycling performances of these samples were also measured at a current density of 100 mA g-1, which is shown in Figure S2. It displays that the sample obtained at 600 oC shows the best electrochemical performance. With increasing temperature of


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calcination, the carbon content in composite decreases. So, the capacity of sample (at 450 oC) is lower due to the higher carbon content. The electrochemical performances of ZnS/NSC are related to the size of ZnS and carbon contents. In addition, A–ZnS/NSC was synthesized similarly with Zinc pyrithione firstly mixed with Na2CO3 (m (Zinc pyrithione) : m (Na2CO3) = 1 : 1.5) at 600 oC for 2 h. 2.2 Material Characterization The crystal structure patterns were carried out by X–ray diffraction (XRD) with Rigaku D/max 2550 VB+ at a scanning rate of 0.1° 2θ s–1. The morphologies and structural characteristics were investigated via utilizing scanning electron microscopy (SEM, JSM–6510LV), transmission electron microscopy (TEM, JEM–2100F) and high–resolution transmission electron microscopy (HRTEM, JEM–2100F). Thermogravimetric analysis (TGA) was conducted within the temperature range from 25 oC to 900 oC on a thermal analysis instrument (NETZSCH STA449F3) at a heating rate of 10 oC min–1 in air. Specific surface areas were got via N2 sorption/desorption analysis on a Micromeritics ASAP 2020 HD analyzer at 77 K. The surface composition analysis was further researched by X–ray Photoelectron Spectroscopy (XPS, ESCALab250) with C1s at 284.6 eV as a reference. Fourier transform infrared spectrophotometer (FT–IR, AVTATAR, 370) was utilized to collect FT–IR spectrums of samples with KBr as a reference. 2.3 Electrochemical Measurements The working electrodes were obtained through a typical synthesis process. Active materials, carboxymethyl cellulose (CMC) binder and super P (at a 75:15:10 weight ratio) were mixed in deionized water. The formed slurries were then homogeneously coated on copper foils and dried


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at 100 °C for 12 h in vacuum. The electrodes were further pressed under a pressure of about 15 MPa. The mass loading is 1.0 ~1.2 mg/cm2. CR2025 coin cells were fabricated in an Ar–filled glove box utilizing a metallic sodium foil as counter and reference electrodes, a solution of NaClO4 in ethylene carbonate and propylene carbonate (1:1 in volume) as electrolyte and a porous polypropylene film as the separator. Cyclic voltammetry (CV) tests at a scanning rate of 0.2 mV s–1 were conducted on MULTI AUTOLAB M204 (MAC90086). Electrochemical impedance measurements (EIS) with the frequency of 100 kHz ~ 0.01 Hz at their open– circuit voltages were conducted on CHI 660B electrochemical working station. Galvanostatic charge/discharge files between 0.01 and 3.0 V (vs Na+/Na) were investigated using Land CT2001A battery cycler. 3. RESULTS AND DISCUSSION Figure 1a shows the XRD patterns of as–prepared ZnS/NSC and A–ZnS/NSC samples. All diffraction peaks of ZnS/NSC can be assigned to the hexagonal ZnS containing the 6H phase (JCPDS No. 89–2191), indicating that the Zn(II) in the molecular structure of Zinc pyrithione is successfully turned into ZnS substance without impurity through a calcination process. The diffraction peaks at A–ZnS/NSC material mainly correspond to the hexagonal structure (2H phase, JCPDS No. 75–1547), while the existence of weak peaks at 36.1o and 69.4o can be indexed to the 6H phase (JCPDS No. 89–2191).32 Meaningfully noting that the crystalline structure of A–ZnS/NSC material is hexagonal structure that contains 2H and 6H polytypes.32 The corresponding ball–and–stick models are shown in Figure 1b. Like other materials,33-34 this mixed–phase could promote the electrical transmission rate. So, this structure could contribute to improve the electrical conductivity of ZnS itself. In addition, the related diffraction peaks of


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NSC has not been observed in Figure 1a. This illustrates the amorphous state NSC was obtained from Zinc pyrithione via calcination.

Figure 1. (a) XRD patterns of ZnS/NSC and A–ZnS/NSC samples. (b) Ball–and–stick models of 2H and 6H of ZnS polytypes. Figure 2 displays the SEM images of ZnS/NSC and A–ZnS/NSC composites. As shown in Figure 2a and c, irregular ZnS particles in ZnS/NSC sample are mainly distributed on the surface of NSC material. The size distribution of ZnS particles in ZnS/NSC (the inset of Figure 2a) illustrates the size of ZnS particles obtained in ZnS/NSC is inhomogeneity and the average size is about 150 nm. While, the A–ZnS/NSC exhibits carbon–encapsulated ZnS nanoparticles as seen from the SEM in Figure 2b and d. The main size of ZnS nanoparticles in A–ZnS/NSC is about 60 nm based on the analysis of the inset of Figure 2b, illustrating the size of ZnS becomes


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small with the introduction of Na2CO3. The smaller size can provide more active sites for electrochemical reaction and the carbon–encapsulated structure might be more effective to relieve volume expansion during Na+ extraction/insertion process. The compositions of ZnS/NSC and A–ZnS/NSC were further analyzed by energy dispersive X–ray (EDX) in Figure S3b and S4b. It reveals that the two composites are both comprised of Zn, S, C and N elements. Figure S3 and S4 display the energy dispersive X–ray spectrometry mapping analysis of ZnS/NSC and A–ZnS/NSC samples to estimate the distribution of elements. Figure S3c–f show that Zn, S and C elements are uniformly and continuously distributed with a small amount of N element, confirming again the components of ZnS/NSC sample. The similar results in Figure S4c–f suggest that the A–ZnS/NSC composite contain ZnS and NSC. All above results illustrate ZnS decorated with N, S co–doped carbon is obtained by calcinating zinc pyrithione without other C, N or S sources.


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Figure 2. (a) and (c) are the SEM images of ZnS/NSC. (b) and (d) are the SEM images of A– ZnS/NSC. The insert pictures correspond to the size distribution of ZnS particles in ZnS/NSC and A–ZnS/NSC composites, respectively.

TEM and HRTEM images of ZnS/NSC and A–ZnS/NSC have been further conducted to investigate the morphology and micro–structure of samples, which were displayed in Figure 3. Compared with Figure 3a and Figure 3b, the morphology structure of A–ZnS/NSC is obviously different from ZnS/NSC. Based on the chemical activation of Na2CO3, carbon–encapsulated ZnS nanoparticles were formed. Figure 3c shows the HRTEM image of ZnS/NSC. The lattice fringes of 0.310 nm are from the (006) plane of 6H crystalline ZnS and the as–formed NSC is


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amorphous. In the HRTEM image of A–ZnS/NSC (Figure 3d), the lattice fringes at 0.332 nm and 0.137 nm correspond to (100) phase of 2H crystalline and (208) phase of 6H crystalline, respectively, which is in perfect accordance with XRD results. Also, the NSC structure in A– ZnS/NSC composite is amorphous state.

Figure 3. (a) and (c) are TEM and HRTEM images of ZnS/NSC, respectively. (b) and (d) are TEM and HRTEM images of A–ZnS/NSC, respectively. Moreover, the contents of NSC in ZnS/NSC and A–ZnS/NSC composites were investigated via TGA operated from 25 oC to 900 oC, which is shown in Figure 4a. The first step of weight less of samples from 25 oC to 150 oC is mainly resulted from adsorbed water.7, 11 The followed step is due to the weight less from coordinated water and oxygen–containing groups in the samples. The third step weight less from 400 to 750 oC is attributed to both oxidation process of ZnS (ZnS + 3/2O2 → ZnO + SO2) and combustion of NSC.11 Based on the final product of


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ZnO,35 the contents of ZnS component in ZnS/NSC and A–ZnS/NSC can be calculated to be approximately 86.9 wt% and 78.7 wt%, respectively, according to the following equention (eqn1):

ZnSwt%

!!"

100

(eqn1)

Therefore, more carbon could remain with the addition of Na2CO3 during the calcination of zinc pyrithione. From the N2 adsorption/desorption isotherms in Figure 4b, the specific surface area (SSA) of ZnS/NSC and A–ZnS/NSC materials are determined to 13.5 m2 g–1 and 59.2 m2 g–1, respectively. The larger SSA of A–ZnS/NSC composite is likely attributed to the smaller size of ZnS nanoparticles and higher content of NSC.

Figure 4. (a) TGA curves of ZnS/NSC and A–ZnS/NSC samples. (b) N2 adsorption/desorption isotherms of ZnS/NSC and A–ZnS/NSC samples. To further confirm the chemical states of as–got materials, the surface chemical status of elements in ZnS/NSC and A–ZnS/NSC were determined by XPS. As shown in Figure 5a, the XPS survey spectra of ZnS/NSC and A–ZnS/NSC samples indicate the presence of Zn, S, C and


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N, which is well in accordance with the EDX mapping analysis. The Zn 2p spectra are presented in Figure 5b. The two peaks at 1021.8 eV and 1044.8 eV correspond to Zn 2p1/2 and Zn 2p3/2 peaks of Zn2+, respectively.36 Figure 5c and d display the S 2p spectra of ZnS/NSC and A– ZnS/NSC. Each spectrum contains eight fitted peaks. The two major peaks at 161.5 eV and 162.5 eV are indexed to S 2p3/2 and S 2p1/2 in ZnS phase, respectively.25 Another two peaks at 163.5 eV (S 2p3/2) and 164.5 eV (S 2p1/2) are assigned to C–S–C covalent bond.23, 37-38 The weak peaks from 167 eV to 170.5 eV are from the C–SOx–C sulfone bridges.22 The N 1s spectra of ZnS/NSC and A–ZnS/NSC are shown in Figure S5. Two fitted peaks at 398.5 eV and 400.3 eV can be assigned to pyridinic–N and pyrrolic–N, respectively.9, 21 Therefore, as–formed carbon is successfully doped by N and S in both ZnS/NSC and A–ZnS/NSC samples. It is expected that the electronic conductivity and total electrochemical capacity storage of samples can be effectively improved because much more defects and active sites could be introduced to the carbon framework through N and S co–doping.10, 30, 39 From the two S 2p spectra, the A–ZnS/NSC composite exhibits much more C–SOx–C bands, which might be due to the existence of extra O source from Na2CO3. Interestingly, the area ratio of S 2p3/2 (161.5 eV) and S 2p1/2 (162.5 eV) in A–ZnS/NSC is lower than that in ZnS/NSC. Based on the normal ratio (2:1, in pure ZnS phase) and previous preliminary explorations,11 it is believed that the smaller ratio might be mainly attributed to the mixed–crystal structure and the stronger interaction between C–S (meaning the possible formation of C–S–Zn bond). Compared to that of the ZnS/NSC composite, the binding energy values of C–SOx–C band significantly increased in A–ZnS/NSC composite, from the insets in Figure 5. This can be contributed to the possible formation of S–O–Zn bonds. Therefore, there is a stronger interaction


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between ZnS and NSC in the A–ZnS/NSC hybrid via the bridges of C–S–Zn and S–O–Zn, which might be probably indispensable for the outstanding electrochemical properties for SIBs.9

Figure 5. (a) XPS survey spectra of ZnS/NSC and A–ZnS/NSC samples. (b) Zn 2p XPS spectra of and A–ZnS/NSC. (c) S 2p XPS spectrum of ZnS/NSC. The inset is magnification from 166.5 eV to 170.5 eV. (d) S 2p XPS spectrum of A–ZnS/NSC. The inset is magnification from 166.5 eV to 170.5 eV. FT–IR spectra of zinc pyrithione, ZnS/NSC and A–ZnS/NSC are shown in Figure S6. After calcination, the characteristic peaks of zinc pyrithione vanished. The characteristic vibrations at about 636 cm–1 still maintained, indicating the formation of ZnS.40 The weak bands at 1200–1600 cm–1 are indexed to stretching modes of aromatic C–N and C–S.41-42 Compared


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with that of ZnS/NSC, the stronger peak at 636 cm–1 of A–ZnS/NSC could be due to the effect of more C–S–Zn bonds. All these results are well accordance with the XRD and XPS analysis. In order to better realize these structural changes, the possible fabricating process of samples is shown in Scheme 1. Pyrolysis of zinc pyrithione could be the first process during the heat– treatment under Ar.43 Then, the Zn–based products were transformed gradually into ZnS nanoparticles and the products including pyrithione were turned into NSC. Finally, the ZnS/NSC and A–ZnS/NSC composites were obtained, which have been confirmed by XRD and HRTEM results. The main functions of Na2CO3 in preparation are embodied from two aspects. On the one hand, the weakly alkaline of Na2CO3 may accelerate decomposition to form small ZnS nanoparticles. On the other hand, Na2CO3 can be as a template for carbon framework and ZnS, like other salts previous reported.44-45 Hence, the carbon–encapsulated structure of A–ZnS/NSC with the smaller size of ZnS was formed. Above all, A–ZnS/NSC with larger SSA and stronger interaction could expose better electrochemical behaviors than those of ZnS/NSC.


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Scheme 1. Schematic representation of ZnS/NSC and A–ZnS/NSC materials. The sodium–ion storage actions of the as–obtained ZnS/NSC and A–ZnS/NSC composites were investigated in sodium half–cells. CV profiles were firstly measured with the potential range from 0.01 V to 3 V (vs Na/Na+) at a scanning rate of 0.2 mV s–1, which is shown in Figure 6a and b. The similar curves of the two composites illustrate the similar electrochemical reactions. The broad peak between 0.2 V and 1.0 V during the first cathodic scan is attributed to the insertion of Na+ into NSC and ZnS, the electrochemical reaction of ZnS, and the formation of solid electrolyte interphase (SEI).8 During the following anodic scanning, a wide anodic peak at about 0.8 V are observed, suggesting that Na+ is extracted by several steps (mainly include dealloying reactions).7 And a strong oxidation peak at about 1.0 V can be ascribed to the conversion reaction.8 In the second scanning cycle, the cathodic peaks below 0.6 V primarily correspond to the reduction of ZnS to metallic Zn and the further alloying reaction with multiple steps.8 Meanwhile, the subsequent CV profiles are overlapped, declaring the good electrochemical reversibility of the working electrodes.46 The first and second charge/discharge profiles of the as–prepared samples are presented in Figure 6c and d, at a current density of 100 mA g–1. The first discharge capacity and Coulombic


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–1

efficiency of ZnS/NSC composite are 896.1 mA h g

and 65.9 %, respectively. And the first

discharge capacity and Coulombic efficiency are 839.6 mA h g–1 and 60.9 % for A–ZnS/NSC composite, respectively. The second discharge capacities of ZnS/NSC and A–ZnS/NSC electrodes are 561.2 mA h g–1 and 516.6 mA h g–1, respectively. The irreversible capacity loss is mainly due to the irreversible formation of SEI layer.6 While A–ZnS/NSC shows a lower discharge specific capacity in the initial cycle than that of ZnS/NSC electrode, which could be due to the higher content of carbon. Compared with some previous reported ZnS–based materials (Table 1), both ZnS/NSC and A–ZnS/NSC display high specific capacity for SIBs. The outstanding storage capacity might mainly benefit from N and S co–doping synergistic effect.


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– Figure 6. (a) CV curves of ZnS/NSC electrode at 0.2 mV s 1. (b) CV curves of A–ZnS/NSC

electrode at 0.2 mV s – 1. (c) The first and second galvanostatic charge–discharge profiles of ZnS/NSC at 100 mA g–1. (d) The first and second galvanostatic charge–discharge profiles of A– ZnS/NSC at 100 mA g–1. The cyclic and rate performances of as–gained ZnS/NSC and A–ZnS/NSC materials are shown in Figure 7. As seen from Figure 7a, the reversible specific capacities of ZnS/NSC electrode are higher than those of A–ZnS/NSC electrode during the initial six cycles. Generally, the capacity of carbon is lower than that of ZnS (theoretical specific capacity 574 mAh g-1).7, 47 The initial capacity of ZnS/NSC is higher than that of A–ZnS/NSC electrode, which is mainly due to the lower ZnS content in A–ZnS/NSC composite. While, the following reversible specific capacities of A–ZnS/NSC are higher than ZnS/NSC, illustrating the A–ZnS/NSC with larger specific surface area and more bridges exhibits much better electrochemical performances. After 100 cycles at a current density of 100 mA g–1, the discharge capacities of ZnS/NSC and A–ZnS/NSC electrodes are 379.9 mA h g–1 (about 67.7% capacity retention) and 500.7 mA h g–1 (about 96.9% capacity retention), respectively. Hence, A–ZnS/NSC exhibits better cycle stability than ZnS/NSC, indicating that the carbon–encapsulated structure can preferably remit the volume expansion of ZnS component during Na+ insertion/extraction process.48 Moreover, the cycling stability of A–ZnS/NSC composite at a high current density of 500 mA g–1 is shown in Figure 7b. The reversible specific capacity maintains 334.5 mA h g–1 (about 81.5% retention rate) after 200 galvanostatic charge–discharge cycles. The Coulombic efficiency quickly increased to 98.2% after eight cycles, suggesting splendid reversibility of electrochemical reaction from A– ZnS/NSC electrode.


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Figure 7c displays the rate capabilities of as–prepared samples. A–ZnS/NSC composite shows much better rate behavior than that of ZnS/NSC. The discharge specific capacities of A– –1

ZnS/NSC composite are 514.8, 465.9, 421.7, 364.9 and 316.1 mA h g

at the current densities

of 100, 200, 400, 800 and 1600 mA g–1, respectively. When the current density got back to 100 mA g–1, the discharge specific capacity returns to 507.5 mA h g–1. The better performances may be mainly attributed to the mixed–crystal structure of A–ZnS/NSC, the larger SSA, and the stronger interaction through bridges between ZnS and NSC. The EIS measurements of electrodes were further conducted at the open–circuit voltages after 100 cycles, which is presented in Figure 7d. Compared with semicircle shapes, the charge transfer resistance (Rct) of A–ZnS/NSC composite is smaller than that of ZnS/NSC composite, confirming the A–ZnS/NSC exhibits much higher charge transfer rate.8


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Figure 7. (a) Cycling performances of ZnS/NSC and A–ZnS/NSC samples at a current density of 100 mA g 1. (b) Cycling performance and Coulombic efficiency of A–ZnS/NSC at 500 mA –

g–1. (c) Rate performances of ZnS/NSC and A–ZnS/NSC samples at different current densities of 100, 200, 400, 800 and 1600 mA g–1, respectively. (d) Nyquist plots of electrodes after 100 cycles. Taking ZnS–based materials as anodes for SIBs reported so far for comparison (in Table 1), the as–prepared A–ZnS/NSC sample shows outstanding cycling stability and rate behavior, which is mainly contributed to the following two factors: (i) N and S co–doping, and (ii) bridges between ZnS and NSC. According to the XPS results, the amounts N- and S- dopants in the surface A-ZnS/NSC composite are about 2.8 wt% and 2.1 wt%, respectively. For the carbon framework, the N and S co–doping can enhance the electrical conductivity, beneficial to promote the electron transfer rate of electrode. Also, more defects and active sites could be introduced to improve the total capacity of the composite because of N and S co–doping.10 Moreover, the existence of C–S–Zn and S–O–Zn bonds in the composite confirmed by XPS analysis is probably helpful for the excellent electrochemical performances. The strong interaction between ZnS and NSC can effectively decrease the aggregation of ZnS nanoparticles during the preparation and cyclical processes. The carbon–encapsulated structure of the hybrid may better tolerate

the

large

volume

expansion

of

the

ZnS

nanoparticles

during

the

intercalation/deintercalation.


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Table 1. Cycling capacity retention and rate behavior of ZnS–based materials between this work and previous reports.

Cycling capacity retention

L–rate capacity

H–rate capacity

(%)

(mA h g–1)

(mA h g–1)

ZnS particles8

15.6, 50 cycles (100 mA g–1)

412 (100 mA g–1)

–

ZnS–RGO8

78.9, 50 cycles (100 mA g–1)

610 (100 mA g–1)

357 (1 A g–1)

ZnS nanospheres (EC/PC)6

~ 15, 30 cycles (80 mA g–1)

~ 400 (80 mA g–1)

–

Materials

ZnS nanospheres (EC/TEGDME)6 Urchin–like ZnS7

~ 84.4, 30 cycles (80 mA g–1)

~ 610 (80 mA g–1) ~420 (0.64 A g–1)

5, 100 cycles (100 mA g–1)

400 (100 mA g–1)

35 (1 A g–1)

Urchin–like ZnS/NC7

79.2, 100 cycles (100 mA g–1)

480 (100 mA g–1)

360 (1 A g–1)

ZnS–Sb2S3@C46

~63.6, 120 cycles (100 mA g–1) 1043(100 mA g–1)

ZnS/NSC (This work)

~ 67.7, 100 cycles (100 mA g–1) 561.2 (100 mA g–1) 315.8 (0.8 A g–1)

390.6 (0.8 A g–1)

96.9, 100 cycles (100 mA g–1) 516.6 (100 mA g–1) 364.9 (0.8 A g–1)

A–ZnS/NSC (This work) 81.5, 100 cycles (500 mA g–1)

4. CONCLUSIONS In summary, ZnS/NSC composite is prepared by direct calcination of Zinc pyrithione. With the introduction of Na2CO3, A larger specific surface area, a higher carbon content and more bridges (C–S–Zn and S–O–Zn bonds) were obtained in A–ZnS/NSC composite. N, S co–doped carbon is


21


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beneficial to enhance the electron transfer rate and improve the specific capacity of composites. The A–ZnS/NSC composite as an anode for SIBs displays much better cycling stability (500.7 mA h g–1 of discharge capacity and about 96.9% capacity retention after 100 cycles at 100 mA g– 1

) and rate behavior (364.9 mA h g–1 even at a high current density of 800 mA g–1) than those of

ZnS/NSC composite, which is mainly due to its mixed–crystal and carbon–encapsulated structure, and the strong interaction between ZnS and NSC. Meaningfully, metal sulfide/carbon composites prepared utilizing sulfur–containing metal complexes as raw material could exhibit strong interaction between metal sulfide and carbon, which might become one effective approach to improve the electrochemical performances for SIBs.


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ASSOCIATED CONTENT Supporting Information. The following files are available free of charge. SEM images of samples obtained at different heat-treatment temperatures; Cycling performances of samples under various heat-treatment temperatures; EDX spectra and element mapping of ZnS/NSC and A–ZnS/NSC; N 1s XPS spectra of ZnS/NSC and A–ZnS/NSC; FI–IR spectra of zinc pyrithione, ZnS/NSC and A–ZnS/NSC; SEM images of samples obtained after cycles. AUTHOR INFORMATION Corresponding Author * Email address: [email protected]; [email protected] ACKNOWLEDGMENT The financial support of National Natural Science Foundation of China (No. 21701044, 51772092), Natural Science Foundation of Hunan Province China (Grant No. 2017JJ3097), and the Research Foundation of Education Bureau of Hunan Province, China (Grant no. 17A086, 16C0717, 17K039). X. C. appreciates the support from the U.S. National Science Foundation (DMR–1609061), and the College of Arts and Sciences, University of Missouri − Kansas City. REFERENCES


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N, S Co-Doped Carbon Composite from Zn

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