Graphene Decorated by Indium Sulfide Nanoparticles as High

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Graphene Decorated Indium Sulfide Nanoparticles as High-Performance Anode for Sodium-Ion battery Xia Wang, Jang-Yeon Hwang, Seung-Taek Myung, Jusef Hassoun, and Yang-Kook Sun ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b05057 • Publication Date (Web): 19 Jun 2017 Downloaded from http://pubs.acs.org on June 21, 2017

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ACS Applied Materials & Interfaces

Graphene Decorated Indium Sulfide Nanoparticles as High-Performance Anode for Sodium-Ion battery Xia Wang1, Jangyeon Hwang1, Seung-Taek Myung2, Jusef Hassoun3*, Yang-Kook Sun1* 1

Department of Energy Engineering, Hanyang University, Seoul, 133-791, South Korea

2

Department of Nanotechnology and Advanced Materials Engineering & Sejong Battery Institute,

Sejong University, Seoul, 05006, South Korea 3

Department of Chemical and Pharmaceutical Sciences, University of Ferrara, Via Fossato di

Mortara, 44121, Ferrara, Italy *Corresponding authors: [email protected]; [email protected] Keywords Graphene; In2S3; Nano-composite; Anode; SIBs Abstract We report a highly performing anode material for sodium-ion batteries (SIBs), composed of graphene decorated by indium sulfide (In2S3). The composite is synthesized by a facile hydrothermal pathway with subsequent annealing, and characterized by defined structure and well-tailored morphology, as indeed demonstrated by X-ray diffraction, spectroscopy as well as high resolution microscopy. These optimal characteristics allow the electrode to perform remarkably in sodium cell by achieving a maximum specific capacity as high as 620 mAh g-1, and the still relevant value of 335 mAh g-1 at an extremely high current (i.e., 5 A g-1). The high storage capacity, the long cycle life and the impressive rate capability of the composite may be attributed to the synergetic effect between uniform In2S3 nanoparticles and graphene matrix. These features suggest the In2S3-graphene a viable choice for application as an anode material in high-performance SIBs. 1

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1. Introduction The large-scale diffusion of lithium-ion batteries (LIBs), i.e., the dominant power source for portable electronic devices, along with the world’s limited lithium reserves have increased the economic impact this system for important applications, such as the energy storage from renewable energy plants, which reasonably requires massive and cheap use of battery.1 Owing to the natural abundance and low cost of sodium, batteries based on this alkali metal, i.e., sodium-ion batteries (SIBs), have been attracting more concerns as promising and acceptable alternatives to LIBs.2 A similar strategy to that adopted for the characterization and the development of LIBs has led to several studies focusing on the electrode materials for application in SIBs. Among the various cathode materials, those based on layered structure3 and olivine structure4 have achieved the best performances, and are nowadays considered as alternative materials for application in efficient sodium battery. In particular, layered sodium-metal oxides, mainly including transition metals such as Ni, Mn and Co, revealed very enhanced characteristics in sodium cell, such as a satisfactory cycling life, and a specific capacity as high as 200 mAh g-1.5 Relevant number of materials, including metals,6,7 metal oxides,8 metal sulfides,9 and metal selenides,10 have been investigated as potential high capacity anodes for SIBs. However, compared to lithium ions, sodium ions possess larger radius and slower reaction kinetics, which lead to huge volume variation and large polarization, hence giving rise to poor cycling performance and low reversible capacities.11,12 Therefore, many challenges have been devoted to the exploitation of host anode materials for sodium with high capacity, excellent rate performance, and good cycling stability. Sodium alloying electrodes13 and transition metal oxides, such as NiO, CuO, Fe2O3,14 gained increasing interest as anode materials due to their favorable electrochemical characteristics in sodium cell. Recently, metal sulfides such as MoS2,15 CoS2,16 Fe1-xS,17 Co3S418 and SnS,19 have attracted relevant attention 2


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for SIBs due to their high theoretical capacity. Metal sulfides react with sodium through a multi-step electrochemical process involving initial ion intercalation and subsequent conversion, i.e., a high capacity multi-electron pathway.20 In particular, In2S3 is characterized by a large number of vacancies and possesses incompletely coordinated sulfur atoms, therefore, it can accommodate massive metal ions to form magnetic and semiconducting materials.21 Therefore, this interesting material has been widely used in solar cells22, lithium ion batteries,23 and environmental photocatalytic studies,24 owing to low toxicity and high theoretical lithium-storage capacity.23 However, In2S3 manifests a remarkable volume variation and consequent structural failure of the electrode during the electrochemical conversion process in lithium cell.25,26 This issue has been actually mitigated by adopting various strategies, including crystal size reduction,27 synthesis of favorable nanostructures28 and of composites in conductive matrix.23 Among the various materials, graphene (GNS) possesses superior electrical conductivity, high specific surface area, robust mechanical stability and excellent chemical stability, and therefore it has been generally considered as an ideal matrix for buffering the mechanical stress exploited during the conversion process.29-31 Reduced graphene oxide-In2S3 composite, in which the In2S3 sheets were vertical to/lie on the reduced graphene oxide matrix, has revealed enhanced cycling stability with respect to the bare In2S3 in lithium cell.23 Furthermore, it has been demonstrated that graphene is favorable to improve the sodium-storage performance of active materials.32 Indeed, a composite material formed by decorating graphene with antimony sulfide nanoparticle has revealed remarkable cycling stability in sodium cell.2 Despite this strategy appears well suitable for application in SIBs, there is a lake of reports, to the best of our knowledge, on In2S3/graphene exploiting the sodium conversion reaction. In2S3 may be expected to have higher cost with respect to various metal sulfides due to the less reserves of indium with respect to other metals, such as nickel, cobalt and manganese. However, 3



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excellent performances in terms of efficient sodium-storage capability of In2S3 and high theoretical capacity may actually justify its possible use in advanced prototypes of sodium-ion batteries characterized by long life, high capacity and remarkable rate capability and hinder the problems associated with the cost. Following this trend, we develop herein a facile hydrothermal-annealing synthesis to in-situ decorate graphene sheets by In2S3 nanoparticles for application as anode in SIBs. The defined structure, and a morphology consisting of well-distributed In2S3 nanoparticles in graphene enhance the electric conductivity of the material and buffer the volume strain during the sodium conversion reaction. Therefore, the In2S3-graphene composite shows a high reversible capacity, excellent rate capability and extended cycling stability. 2. Experimental 2.1 Preparation of the In2S3-graphene composite Graphene oxide (GO) was synthesized by a modified Hummers method.29 The indium sulfide-graphene

composite

(In2S3-graphene

composite)

was

prepared

via

two-step

hydrothermal-calcined pathways. In overall, 20 mL of as-synthesized GO suspension (6 mg mL-1) was dispersed into 40 mL of DI water and ultrasonicated for 3 h. Subsequently, 0.4 g of indium chloride (InCl3, Sigma-Aldrich) and 2 g of thioacetamide (TAA, Sigma-Aldrich) were added into the above GO suspension. The mixture was sonicated for 1 h, and transferred into a 100 mL Teflon-lined stainless steel autoclave, maintained at 180 oC for 24 h. The resulting powder was centrifuged and washed with distilled water and absolute ethanol for 3 times, respectively. The obtained material was dried at 50 oC for 12 h, and calcined at 400 oC for 3 h under nitrogen atmosphere. For comparison, bare In2S3 powder without addition of graphene was prepared by using the same synthetic route. 4


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2.2 Characterization of the In2S3-graphene composite The phase composition and purity of the as-prepared samples were determined by powder X-ray diffraction (XRD) with Cu Kα (λ = 1.54178 Å) incident radiation using a XRD, Rint-2000, Rigaku. The morphology of the samples was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM), which were taken on JEOL JSM-6400 SEM unite and JEOL-2010, respectively. The Brunauere Emmette Teller (BET) surface area of the samples was characterized by a Quantachrome Autosorb-iQ-MP surface area detecting instrument with N2 physisorption at 77 K.

X-ray photoelectron spectroscopy (XPS, PHI 5600, PerkinElmer, USA)

measurements were performed in order to detect oxidation state of transition metals. Thermogravimetric analysis (TGA) was carried out under air flow by a TG 209, Netzsch, Germany. Raman spectroscopy was performed using a Renishaw spectrometer with the laser line of 532 nm, and by a WITec CRM200 confocal Raman microscopy system at a laser wavelength of 488 nm and a spot size of 0.5 mm. 2.3 Electrochemical Characterization Electrochemical tests were carried out in CR2032 coin-type cells using Na metal (Aladdin) as the counter electrode. The working electrode were prepared by mixing the In2S3-graphene composite,

carbon

black

(Sigma-Aldrich),

and

carboxymethylcellulose

sodium

(CMC,

Sigma-Aldrich) binder with a weight ratio of 70:20:10 (wt%) to form a slurry. The slurry was then cast by doctor-blade on copper foil and dried at 110 °C for 12 h in a vacuum oven. The final electrode loading was of 1.0-1.6 mg/cm2). The electrolyte solution used was 1.0 M NaClO4 (Sigma-Aldrich) in a 1:1 volumetric mixture of propylene carbonate and ethylene carbonate (Sigma-Aldrich) with 5% fluoroethylene carbonate (Sigma-Aldrich) additive. All cells were 5



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assembled in an Ar filled dry box with water and oxygen content lower than 1 ppm. Cyclic voltammetry (CV) was performed using an Arbin BT-2000 battery tester (Arbin Instrument) at a scanning rate of 0.2 mV s-1 within a potential range of 0.001−3.0V versus Na at room temperature. The cells were galvanostatically cycled within 0.001V and 3.0V using various currents at room temperature. Electrochemical impedance spectroscopy (EIS) was performed upon cell cycling using an Arbin instrument in a 100 kHz – 0.01 Hz frequency range, with a bias signal amplitude of 0.01V. 3. Results and discussion Figure 1 illustrates the synthesis rout adopted for the preparation of the In2S3-graphene composite (see experimental section for details). Due to the presence of substantial functional groups including carboxyl and hydroxyl groups on the surface of GO sheet, TAA tends to be grafted on the GO via amino groups activated by the C=S bonds.33 In spite, In3+ may be electrostatically attracted by the above mentioned electron-rich surface groups of the GO sheet. During the hydrothermal process, TAA releases S2- under alkaline conditions through hydrolysis, which then reacts with the adsorbed In3+ to form In2S3 nuclei tightly anchored and well dispersed onto GO sheet (In2S3-GO precursor). The final annealing step at 400oC leads to the In2S3-GO material, in the form of a black powder composed of graphene networks decorated by In2S3 nanoparticles. Figure 2a depicts the XRD pattern of the In2S3-graphene composite. All the diffraction peaks can be assigned to the tetragonal In2S3 (JCPDS No. 25-0390) without relevant impurity signals, while the absence of reflections due to the graphene mostly reflects its very modest crystallinity.33 Furthermore, the EDS of the composite (Figure 2b) suggests the presence of In, S, O and C elements.

6


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Figure 1. Schematic illustration of the synthesis procedure of the In2S3-graphene composite. The graphene was further confirmed by two characteristic Raman peaks at 1330 and 1590 cm-1 (Figure 2c), corresponding to the disordered carbon (D band) and ordered graphitic carbon (G band), respectively.29 The peaks at 244 and 306 cm-1 in the Raman spectrum may be assigned to the symmetric stretching vibrations of InS6 octahedra and InS4 tetrahedra of In2S3, respectively,34,35 while the peaks at 494 and 630 cm-1 can be ascribed to In2O3 due to partial surface oxidation of the composite.36 The graphene content is further confirmed by TGA (Figure 2d) which reveals a weight change of about 3% between 25 and 200 oC, corresponding to absorbed water loss, and an approximate 24% decrease from 200 to 800oC, attributed to the oxidation of In2S3 and combustion of the carbon from the composite, as indeed observed for analogue metal sulfides/carbon.7 The XRD pattern of the oxidation product after TGA shown in Figure S1 in Supporting Information confirms that the final product of In2S3 oxidation is In2O3 (JSCPDF No. 65-3170). Therefore, according to TGA and XRD results, the content of carbon in the indium sulfide-graphene composite was calculated to be 11.5 wt%.

7



(b)

(109)

In2S3/GNS

Si S

PDF 25-0390

In

(2212)

(0012)

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(a)

(1015)

(419)

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(316)

(206)

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6 2.8%

(d) 1330

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80

60

494 630

40 300

600 900 1200 1500 1800 -1 Raman shift (cm )

0

200 400 600 o Temperature ( C)

800

Figure 2. (a) XRD pattern, (b) energy dispersive spectroscopy (EDS) spectrum, (c) Raman spectrum and (d) thermogravimetric analysis (TGA) profile of the In2S3-graphene composite. Electronic state and composition of the material under study are detected by XPS (Figure 3). The survey spectrum (Figure 3a) reveals the presence of In, S and C elements, in agreement with the EDS result. The atomic ratio of In and S is estimated to be of around 13% and 18% according to the XPS quantitative analysis, while the ratio of In and S elements in XPS survey spectra is calculated to be about 0.74, which is higher than the 0.67 expected by the In2S3 stoichiometry, as most likely ascribed to the above mentioned presence of In2O3 in the sample. Besides, the high-resolution O 1s XPS spectrum (Figure S2 in Supporting Information) exhibits two peaks at 531.3 and 532.3 eV, corresponding to O-atoms in the vicinity of an O-vacancy of the In2O338 and residual oxygen bonded to carbon in graphene, respectively, which confirms the presence of traces 8


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of In2O3 in the In2S3-graphene composite, due to partial surface oxidation. On the basis of the XPS, the weight ratio of In2S3 and In2O3 in the sample is estimated to be of approximately 11:1. The high-resolution In 3d spectrum (Figure 3b) exhibits two characteristic peaks of In2S3 at 444.7 eV (In 3d5/2) and 452.3 eV (In 3d3/2), which agree well with the values for In3+.37 The S XPS peaks at 161.3 and 162.6 eV in the S 2p spectrum of Figure 3c (S 2p3/2 and S 2p1/2 of S2-) further confirms the In2S3 stoichiometry.37 The graphene may be identified by the three XPS peaks of C 1s centered at 284.6, 285.9 and 288.7 eV (Fig. 3d), corresponding to sp2 C-C, C-O and O-C=O bonds, respectively.29 Therefore, the XPS data well confirm the formation of In2S3-graphene composite. In3d

(a)

5/2

In3d3/2

In

(b)

In2p In3d1/2 3/2 O1s C1s S2s S2p3/2

800

600 400 200 Binding energy (eV) 2-

S

(c)

168

Raw data S2p3/2

456

2-

S

S2p1/2

Raw data In3d 3/2

453

450 447 444 Binding energy (eV)

Raw data C-C C-O O-C=O

291

165 162 159 Binding energy (eV)

441

C1s C 1s

(d)

S 2p

In 3d

In3d 5/2

Intensity (a.u.)

1000

3+

3+

Intensity (a.u.)

Intensity (a.u.)

In

Intensity (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


288 285 282 279 Bingding energy (eV)

Figure 3. (a) Survey and (b-d) high-resolution XPS spectra of the In2S3-graphene composite, respectively. Figure 4 shows the morphological characteristics of the composite as determined by SEM, TEM and HRTEM. The study suggests the presence of rough graphene sheets (Figure 4a) over 9



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which In2S3 nanoparticles are decorated (Figure 4b). Furthermore, the TEM images (Figure 4c,d) indicate a uniform dispersion and an average size of 40 nm for the In2S3 particles on the graphene. The HRTEM images (Figure 4e and inset) reveal two lattice fringes of 0.183 and 0.259 nm size attributed to the (413) and (224) planes of In2S3, as long as the corresponding diffraction rings (Figure 4f) suggest the polycrystalline nature of the composite. Meanwhile, the element mappings suggest In, S and C uniformly distributed within the selected structure (Figure 4g–j).

Figure 4. (a,b) low- and high-magnification SEM images, respectively, (c,d) low- and high-magnification TEM images, respectively, (e and inset) high-resolution TEM (HRTEM) images, (f) selected area electron diffraction pattern (SAED), (g) scanning transmission electron microscopy (STEM) image and corresponding element mappings of (h) In, (i) S, (j) C of the In2S3-graphene composite, respectively. 10


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The porous nature of the In2S3-graphene composite, i.e., an important parameter for allowing its optimal operation in cell, is revealed by N2 adsorption-desorption isotherms and the corresponding pore size distribution (Supporting Information Figure S3). The In2S3-graphene composite shows the typical IV isotherms with a large hysteresis loop in the pressure range of 0.4-1.0 (P/P0), thus indicating the presence of mesopores (Figure S3a).39 Meanwhile, a wide pore size distribution with average size of about 20 nm is measured by the Barrett-Joyner-Halenda (BJH) method (Figure S3b). The BET surface area is calculated to be of about 56 m2 g-1, that is, a relatively high value which may provide a suitable contact area between the electrode and electrolyte, as well as short ion and electron diffusion paths. These characteristics are expected to allow enhanced performance of the electrode, such as high capacity and remarkable rate capability.40 The electrochemical performances of the In2S3-graphene electrode are evaluated in sodium cell. The electrochemical process of the material is investigated by CV and reported in Figure 5a. The 1st cathodic scan exhibits broad, low intensity irreversible reduction peaks ranging from 1.5V to 1.1V vs. Na+/Na which may be likely attributed to the decomposition of electrolyte and the formation of the solid electrolyte interface (SEI) films.3,14,41 A further reduction of the potential below 1V vs Na+/Na leads to an intense peak due to the conversion reactions of In2S3 into Na2S and In (i.e., In2S3+6Na ⇄ 2In+3Na2S), analogously to the process occurring in lithium cells.23 However, partial sodium insertion into In2S3 structure at the higher potentials and in the carbon matrix at the lower ones cannot be excluded. The 1st anodic scan shows various peaks in the potential region ranging from 0.3V to 1.7V vs. Na+/Na. Despite these peaks may be reasonably ascribed to the multistep oxidation of In with formation of In2S3 (i.e., 2In+3Na2S ⇄ In2S3+6Na), a low potential de-insertion of Na from carbon and a high potential conversion of Na2S to S and Na cannot be excluded.42 The 11



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oxidation peaks are almost completely reversed between 1.2V and 0.1V vs. Na+/Na during the subsequent reduction which shows a different profile with respect to the first one, most likely due to the activation of the material upon the structural changes induced by the conversion/de-conversion processes, as already observed for Sb2S32 and CoSe243 in sodium cell. After the first cycle, the CV profiles progressively overlap with some slight modification by electrode rearrangement, thus suggesting substantial reversibility of the electrochemical process and structural stability of the In2S3-graphene composite.2 The galvanostatic charge/discharge profiles of the electrode in sodium cell cycled at a current of 200 mA g-1 (Figure 5b) almost completely reflect the CV signatures. The 1st discharge delivers a capacity of about 852 mAh g-1 upon a flat plateau evolving below 1V, while a capacity of about 561 mAh g-1 is recovered by charge with a sloping curve from 0.3 to 1.7V, with a resulting Coulombic efficiency of about 66%. The low initial efficiency is attributed to the above mentioned formation of SEI film33 as well as to the structural re-organization of the electrode upon conversion.43 The second discharge evolves by a slope from 1.2V to about 0.1V and delivers a capacity of 600 mAh g-1, while the subsequent charge shows unchanged profile and a capacity of 595 mAh g-1, i.e., a slightly higher value due to material activation already discussed by CV. The subsequent cycles are almost completely overlapped and centered at a voltage value of about 1V, however with the typical charge/discharge hysteresis of electrode exploiting the conversion reaction.41,43 The trend of the delivered capacity and efficiency over the 60 cycles at 200 mA g-1 is reported in Figure 5c. The graph reveals a steady state capacity as high as 550 mAh g-1, a retention of 92% over the test and an efficiency raising by the ongoing of cycles up to 99%. This outstanding performance, in contrast to the very poor trend of a bare In2S3 (Figure S4, Supporting Information), suggests the graphene decoration by In2S3 as suitable strategy for achieving a high performance material for sodium battery. By contrast, pure rGO without indium sulfides tested under the same 12


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conditions presented a low capacity of 160 mAh g−1 after 100 cycles (Figure S5a in Supporting Information), thus revealing the prominent contribution of In2S3 in the composite electrode. Furthermore, the contribution of In2O3 to sodium-storage process has been studied using this material as the working electrode in a sodium half-cell, cycled at a current density of 200 mA g-1 in the voltage range of 0.001-3 V (Figure S5b in Supporting Information). The figure shows a reversible capacity of the order of 100 mAh g-1 after 100 cycles. Considering the very modest capacity achieved by In2O3, and its low weight ratio with respect to In2S3, i.e., 1:11 indicated in the above response, we can conclude that the contribution of In2O3 to the overall electrode capacity may be actually neglected. Besides, the improvement of the achieved by the In2S3-graphene composite may be in part justified by an optimal electrode/electrolyte interface, as indeed shown by EIS of the sodium cell using it upon 60 cycles at 200 mA g-1 (Figure 5d). The Nyquist plot shows a depressed semicircle due to the SEI film (high-frequency), and charge transfer within the electrode/electrolyte interface (middle frequency), as well as a tilted line in the low frequency region due to the Warburg-type semi-infinite diffusion of Na+ within the electrode.13 The analysis of the plot suggests an overall interface resistance as low as 35 Ω. Instead, the bare In2S3 material reveals upon the same test an interface resistance as high as 145 Ω (Figure S6 in Supporting Information). It is noteworthy that reversible capacities of 520, 490 and 370 mAh g-1 are retained with only minor decay over 100 cycles, by increasing the current up to 500, 1000 and 3000 mA g-1, respectively (Figure 5e). The relevant rate capability of the In2S3-graphene electrode is further confirmed by Figure 5f and Figure S7 (Supporting Information) reporting the test at progressively increasing currents. The figure reveals the remarkable capacity of 620 mAh g-1 at low current (100 mA g-1), the well significant value of 335 mAh g-1 at extremely high current (5000 mA g-1), and the almost complete recovery of 13



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the pristine capacity by lowering back the current to the initial value. Figure S8 in Supporting Information reports the long-term performance in of the In2S3-graphene composite sodium cell at two current densities, i.e., 500 mA g-1 during the in initial 100 cycles and 2000 mA g-1 during the subsequent cycles. The figure shows that the cell holds a specific capacity of approximately 420 mAh g-1 after 250 cycles at the higher current value. Remarkably, the TEM images of the In2S3-graphene electrode after 100 cycles in sodium cell (Figure S9 in Supplementary Information) still reveal In2S3 nanoparticles decorated on the graphene sheets, which is the initial composite architecture, thus further demonstrating the remarkable stability upon cycling of the anode material. In contrast, the bare electrode In2S3 shows relatively poor rate capability and relevant capacity fading (Figure S10 in Supporting Information). The enhanced cell performances of In2S3-graphene electrode may be explained by the short diffusion pathway for Na+ ions, the high electronic conductivity and the remarkable buffer effect for the structural changes provided by the graphene into the composite.33 These features locate the electrode studied herein within the top-rank anode candidates for application in SIBs, as indeed demonstrated by the Ragon plot in comparison with other candidates taken from literature references (Figure S11 and Table S1 in Supplementing Information).33,42,44-50

14


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0.0

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150 0

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20 30 40 Cycle number

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-1

-1

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50 00 *

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Coulombic efficiency (%) -Zim (Ω)

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st

1 nd 2 rd 3 th 60

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70

80

Figure 5. Electrochemical performances of the In2S3-graphene electrode in sodium cell. (a) Cyclic voltammetry curves during the initial 5 scans at a rate of 0.2 mV s-1. (b) Galvanostatic charge/discharge voltage profiles at 200 mA g-1 during the 1st, 2nd and 60th cycles, (c) corresponding capacity retention with Coulombic efficiency trends, and (d) EIS Nyquist plots performed from 100 kHz to 0.01Hz using 0.01V signal after the 60 cycles. (e) Cycling performance at high currents, i.e., 500, 1000 and 3000 mA g-1. (f) Rate capability test at current density increasing from 200 mA g-1 to 5 A g-1. Voltage range 0.001V and 3V. Room temperature.

15



1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Figure 6 reports our attempt to study the sodium-storage mechanism of the In2S3-graphene composite upon cycling by ex-situ XRD and HRTEM images. The XRD patterns of the electrode at selected discharge and charge voltages during the 1st cycle between 0.001 and 3 V, show the vanishing of all diffraction peaks related to In2S3 between 0.41 V (state indicated by D0.41) and 0.001 V (indicated by D0.001) during discharge. Beside the peaks of the support (Cu), the figure reveals during the same process the appearance of peaks most likely associated with metallic In and Na2S, which may probably suggest the conversion reaction In2S3+6Na → 2In+3Na2S, however noise and low intensity of the signal avoid the accurate determination of the formed products. It is worth mentioning that the increase of the voltage during charge (C0.49, C1.24, C3, i.e., to 0.49 V, 1.24V and 3V, respectively) slightly modifies the intensity of the new peaks, however the signal of In2S3 is not recovered back, thus likely suggesting remarkable reduction of the grain size or possible amorphization by cycling of the composite which avoids a proper determination of the formed products. The same trend is observed in Figure 6a for the XRD of the electrode charged up to 3 V during the 2nd cycle (C3-2nd). In order to further investigate the reaction mechanism, the electrode is cycled for 100 cycles and HRTEM images are collected at the end of the test, both at the reduced state at 0.001 V (Figure 6b) and at the oxidized state at 3V (Figure 6c and 6d). Figure 6b exhibits three crystal distances for the discharged electrode, i.e., 0.232, 0.227 and 0.245 nm, thus suggesting the presence of Na2S and In, while the charged electrode reveals two crystal lattices with spacing of 0.206 nm (Figure 6c) and 0.225 nm (Figure 6d), corresponding to the In2S3 (1015) and In (200) planes, respectively. According to the above results, we may speculate that the Na-storage of the In2S3-graphene can follow the mechanism proposed by literature, i.e., In2S3+6Na ⇄ 2In+3Na2S,23 however further proofs and more detailed study are certainly required to clearly elucidate the reaction pathway. 16


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⊕ In2S3 & In Φ Na2S

(b)

Cu

Cu

& & Φ Cu

C3-2nd Φ C3

Intensity (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


C1.23 C0.49 D0.001 D0.41 D0.92 Pristine

10

20

⊕

30

⊕

⊕

40 50 60 2θ (degree)

70

80 80

(c)

(d)

Figure 6 (a) ex-situ XRD patterns of the In2S3-graphene electrodes in various discharged/charged states for the 1st cycle and charged to 3 V for the 2nd cycle; HRTEM images of the In2S3-graphene electrodes upon 100th cycle: (b) discharged to 0.001 V, and (c,d) charged to 3 V.

4. Conclusion In summary, the In2S3-graphene composite has been successfully synthesized by in-situ solvothermal/annealing method, and investigated as anode material for SIBs. Detailed structural, morphological and spectroscopic characterization suggested a composite material formed by graphene matrix uniformly decorated by In2S3 nanoparticles. The electrochemical evaluation revealed the composite architecture well suitable for achieving outstanding performances in terms of high delivered capacity (620 mAh g-1), stability and impressive rate capability (up to 6 Ag-1). Therefore, the material is considered a promising candidate for application in next generation sodium-ion battery. 17



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Supporting Information

XRD pattern of the oxidation product after TGA of the In2S3-graphene composite; High-resolution O1s XPS spectrum of the In2S3-graphene composite; N2 adsorption-desoprtion isotherms and BJH pore size distribution of the In2S3-graphene composite; Galvanostatic cycling performance of a bare In2S3 electrode in sodium cell at a current density of 200 mA g-1 in the voltage range of 0.01-3.0 V at room temperature; Cycling performance of the rGO at a current density of 200 mA g-1; Comparison of EIS Nyquist plots performed from 100 kHz to 0.01 Hz using 0.01V signal of the In2S3-graphene composite and bare In2S3 after 60 charge discharge cycles at 200 mA g-1 within a 0.001-3.0 V range at room temperature; Charge/discharge profiles of the In2S3-graphene composite at various current densities, within a 0.001-3.0 V range at room temperature; Cycling performance of the In2S3-graphene composite at 500 mA g-1 for the initial 100th and 2000 mA g-1 for subsequent 150 cycles; Different magnification TEM images of the In2S3-graphene composite electrode after 100 cycles; Rate capability of the bare In2S3 within a 0.001-3.0 V range at room temperature; Ragone plots of the In2S3-graphene composite electrode and other metal sulfide-graphene based anode materials for SIBs taken from the literature.

Acknowledgement

This work was mainly supported by the Global Frontier R&D Program (2013M3A6B1078875) of the Center for Hybrid Interface Materials (HIM) funded by the Ministry of Science, ICT & Future Planning and a National Research Foundation and also supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MEST) (No. 2014R1A2A1A13050479). 18


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Table of content image 1500

3.0

Voltage (V)

2.4

1200 -1

Capacity (mAh g )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

900 500 mA g

600

-1

1000 mA g

300

1.8 1.2

1

0.6 0.0 0

st

300 600 900 -1 Capacity (mAh g )

-1

3000 mA g

-1

Na/In S -graphene

0

2

0

20

3

40 60 Cycle number

80

100

26


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Graphene Decorated by Indium Sulfide Nanoparticles as High

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