A new method of synthesis of Sb₂Se₃/rGO as a high-rate and low-temperature anode for sodium–ion batteries

Abstract

Sodium–ion batteries (SIBs) are expected to replace lithium–ion batteries with low cost and high safety to become a new generation of energy storage equipment. Here, a novel precipitation transformation method is used to synthesize Sb₂Se₃ wrapped by reduced graphene oxide (rGO) as an anode for SIBs. These Sb₂Se₃ nanoparticles with a large surface area and multiple active sites can accelerate sodium ion diffusion and storage, resulting in high capacity and excellent rate performance. At the same time, rGO can alleviate the particle agglomeration of Sb₂Se₃ caused by volume expansion and increase the conductivity of the compound to improve charge transport. This synthesis method enables nanoscale and tight integration with rGO, synchronously satisfying the fast transport of ions and electrons, which provides conditions for the development of low-temperature performance. More importantly, Sb₂Se₃/rGO exhibits a capacity of 260 mA h g⁻¹ at a current density of 20 A g⁻¹ at room temperature. Even at −15 °C, the capacity retention remains at 38% at a current density of 2 A g⁻¹. Therefore, this precipitation transformation method can provide new ideas for synthesizing other compounds.

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Introduction

Lithium-ion batteries as clean energy storage equipment have received extensive attention.^1–3 However, the lack of lithium resources limits the application of lithium-ion batteries in large-scale energy storage equipment. Sodium–ion batteries (SIBs) are promising energy cells because of the similarity of sodium ions to lithium ions and the advantages of rich and inexpensive sodium resources. The application of SIBs is still limited by low energy density/power density, poor low-temperature performance and so on.^4–7 Due to geographical location and climate, the temperature varies widely among regions. A battery may need to work in extreme environments, so exploring low-temperature battery materials is essential.^8,9 For the anode materials, the kinetics of sodium ions insertion is sluggish at low temperature (LT). There is a problem of asymmetry in charging and discharging, and the electrode material is heavily polarized at a high current density.^10,11 Therefore, it is urgent to improve the electrochemical performance at LT.

Compared with the low-capacity de-intercalation mechanism of carbon materials and the alloy-mechanism materials with large volume expansion, transformation mechanism materials can exhibit high capacity with relatively small volume expansion.^12,13 Common anode materials include oxides and sulfur (selenides). Sulfur (selenides) has higher reaction reversibilities and higher Coulombic efficiencies compared with oxides. Sb₂Se₃ can also work as an anode material with a theoretical specific capacity of 670 mA h g⁻¹, which is unmatched by carbon materials.^14–17 Moreover, both the conversion and alloy reactions are involved in the sodiation/desodiation process of Sb₂Se₃.^18,19 The product of the conversion reaction can be used as a buffer material for the alloy reaction to reduce the stress during particle pulverization. LT batteries require higher ionic and electronic conductivity of electrode materials. On the one hand, a composite with carbon material can improve the conductivity of the material and realize the rapid conduction of electrons.^20,21 On the other hand, nanoscale materials can shorten the ion transport path and achieve fast conduction of sodium ions.^15,22–24

However, based on the crystal growth law of antimony selenide, it is easy to grow large rods and difficult to synthesize nanoparticles.^24,25 Ou et al. synthesized a reduced graphene oxide (rGO)-overcoated Sb₂Se₃ nanorod anode for Na⁺ battery, with a linear length of ≈600 nm and a diameter of ≈50 nm. After combining with rGO, the cycling performance of Sb₂Se₃/rGO is greatly improved, but due to the large Sb₂Se₃ nanorods, the rate performance is not satisfactory. At a current density of 2 A g⁻¹, the capacity retention was only 34% compared to that at 0.1 A g⁻¹.¹⁵ Then, Fang et al. developed an ion-exchange method to synthesize Sb₂Se₃ microclips based on a microbelts template. Sb₂Se₃@PPy microclips exhibited improved cycling and rate performance. However, this anisotropic hollow structure is easily collapsed during cycling and agglomerates, thus hindering ionic conduction, and does not exhibit good electrochemical performance.²² Therefore, it is important to use a new method to synthesize carbon–Sb₂Se₃ composite nanoparticles, to achieve fast conduction of ions and electrons simultaneously at LT.^26–30

Here, a new precipitation transformation method is used to synthesize Sb₂Se₃ wrapped by rGO with controllable shape and size. The size of Sb₂Se₃ is only about 10 nm; such small nanoparticles with a large surface area can accelerate the reaction kinetics of sodium ion diffusion and storage, leading to high capacity and good rate performance. The addition of graphene can increase the conductivity and alleviate the particle agglomeration caused by volume expansion of Sb₂Se₃ in cycling. This structure design can realize fast conduction of electrons and ions, which is conducive to electrochemical performance.

Experimental section

Material synthesis

Sb₂Se₃/rGO was fabricated by a precipitation transformation method. Firstly, SnSe nanosheets were synthesized at room temperature. 79 mg Se and 20 g NaOH were dissolved in 50 ml deionized water. Secondly, 0.45 g SnCl₂·2H₂O and 10 g citric acid were dissolved in another 50 ml deionized water. The latter solution was added dropwise into the former under stirring until the solution turned black. SnSe nanosheets were collected by centrifugation, washing, and drying at 60 °C in a vacuum overnight. Next, graphene was obtained from graphite (Sinochem) using a modified Hummers’ method,³¹ and then 30 mg graphene and 0.1 g SnSe nanosheets were dissolved in 30 ml deionized water. 0.114 g SbCl₃ was dissolved in 10 ml alcohol and then added to the former solution under stirring. The solution was transferred into a Teflon-lined stainless autoclave and heated at 120 °C for 12 h. After centrifuging, washing, and drying, the powders were annealed at 400 °C for two hours in Ar/H₂ (95 : 5).

Structural characterization

X-Ray diffraction (XRD) patterns were acquired with an X-ray diffractometer (Bruker D8 Adv, Germany). X-ray photoelectron spectroscopy (XPS) data were obtained with an X-ray photoelectron spectrometer (ES CALAB250, USA). Transmission electron microscopy (TEM), high-resolution TEM (HRTEM), energy-dispersive X-ray spectrometry (EDS) as well as elemental mapping were conducted with transmission electron microscopes (JEOL GEM1011 or JEOL GEM-2100F, Japan). Scanning electron microscopy (SEM) images were obtained with a field-emission scanning electron microscope (Zeiss SUPRA55, Germany). Thermogravimetric analysis (TGA) was conducted with a Mettler Toledo TGA/SDTA851 thermal analyzer from 40 °C to 700 °C in air. N₂ sorption isotherms were performed with a Builder ASAP 2020 HD88 physisorption analyzer at 77 K.

Electrochemical measurements

The sodium-storage performances of the samples were tested with CR2032 coin cells. The working electrode was made of 70 wt% of the active materials, 20 wt% acetylene black, and 10 wt% of sodium alginate. The blend was milled for 30 min with droplets of deionized water to get a slurry. The slurry was spread on a clean copper foil and dried overnight in a vacuum at 60 °C. The loading mass of the active material was about 1 mg cm⁻². Coin cells were assembled using an Ar-filled glovebox (Mikrouna, Super 122017501900). 1.0 M NaClO₄ in ethylene carbonate and dimethyl carbonate (volume ratio of 1 : 1) containing 5% fluoroethylene carbonate was the electrolyte, Whatman GF/F glass microfibers were the separator, and Na foil was the counter and reference electrodes. Cyclic voltammetry (CV) curves were obtained using an electrochemical workstation (LK200A, China) at room-temperature. Galvanostatic discharge/charge profiles were measured on Land battery cyclers (Land CT2001A, China) between 0.01 and 2 V for SnSe nanosheets and 0.01 and 2.5 V for Sb₂Se₃/rGO at different temperatures. Electrochemical impedance spectra (EIS) were collected with an electrochemical workstation (Autolab PGSTAT 302N) in the frequency range of 100 kHz to 0.01 Hz.

Results and discussion

Sb₂Se₃/rGO was synthesized via a precipitation transformation method, as illustrated in Scheme 1. First, pure SnSe nanosheets (Fig. S1 and S2, ESI†) were synthesized in a simple room-temperature method.³² The SnSe nanosheets showed a size distribution with diameters of ∼70 nm (Fig. S3, ESI†). Then Sb₂Se₃/rGO was made by adding SbCl₃ and graphene via a solvothermal reaction at 120 °C. The conversion mechanism is that the concentration of SbCl₃ is very large, and it reacts with Se²⁻ dissociated from SnSe. With the consumption of Se²⁻, the reaction to form Sb₂Se₃ is promoted. As long as the content of Sn in the final component is not high, less than the Ksp of SnSe,¹⁵ it exists in the form of ions and can be removed after washing steps. Finally, the composite was calcined at 400 °C in Ar/H₂, leading to the reduction of graphene to rGO.

Scheme 1 The preparation process of Sb₂Se₃/rGO.

The physical and chemical properties of the material are shown in Fig. 1. Fig. 1a shows the XRD pattern of Sb₂Se₃/rGO. It is noted that all the reflections come from the orthorhombic Sb₂Se₃ phase (JCPDS card no. 72-1184).¹⁵ The peak at 26° originated from rGO, indicating the presence of rGO in the composite.^33,34 Further evidence comes from XPS spectra of Sb₂Se₃/rGO. Fig. 1b shows two peaks at 55.18 and 56.2 eV, which can be attributed to Se 3d_3/2 and Se 3d_5/2, respectively, indicating the presence of Se²⁻ in Sb₂Se₃.³⁵ As shown in Fig. 1c, the two peaks at 530.9 and 540.2 eV are assigned to Sb 3d_3/2 and Sb 3d_5/2 of Sb³⁺ in Sb₂Se₃. Another peak at 533.2 eV corresponds to O 1s, which can be attributed to the lesser oxidation of Sb₂Se₃ nanoparticles.²³ There are four peaks located at 284.6, 285.2, 286.6, and 289.2 eV from the high-resolution XPS spectrum of C 1s, owing to SP²⁻ bonded C–C, SP^3- bonded C–C, C=O and O=C–O, respectively (Fig. 1d).^28,36 The content of Sb₂Se₃ in the composite was examined by TGA. Fig. 1e shows the weight gain before 400 °C, assigned to the oxidation of Sb₂Se₃ to Sb₂O₄ and SeO₂. Next, weight loss is associated with the sublimation of SeO₂ and the oxidation of rGO (Fig. S4, ESI†). Through calculation, the content of Sb₂Se₃ in the composite is about 81 wt%. This result is in good agreement with the EDS spectrum (Fig. S5, ESI†). As shown in Fig. 1f, the specific surface area of Sb₂Se₃/rGO is measured by nitrogen adsorption–desorption isotherm, with a specific surface area of 58.3 m g⁻² and an average pore size of ∼25 nm, created by particle stacking. Although the large specific surface area reduces the initial Coulomb efficiency, it dramatically increases the migration speed of sodium ions.

Fig. 1 Structural characterization. (a) XRD pattern. XPS spectra of (b) Se-3d; (c) Sb-3d; (d) C-1s of Sb₂Se₃/rGO. (e) TGA curve. (f) N₂ sorption isotherms and pore size distribution of Sb₂Se₃/rGO.

The morphology characterization is shown in Fig. 2. Fig. 2a and b show SEM images of nanoparticles that are uniformly distributed on the surface of rGO. As shown in Fig. 2c and d, the size of Sb₂Se₃ nanoparticles is ∼10 nm, and the tiny size could lead to large surface area, which is well matched with the better electrochemical performance. HRTEM image (Fig. 2e) shows clear lattice fringes with a spacing ∼0.316 nm that could be attributed to (211) planes of Sb₂Se₃, which is in agreement with the XRD results in Fig. 1a. EDS element mapping can further reveal that both Sb and Se are uniformly distributed throughout the rGO, as illustrated in Fig. 2f. The size of Sb₂Se₃ is controllable through the adjustment of concentration, reaction time and temperature. The different size of Sb₂Se₃ particles means that the reaction kinetics is inconsistent, which in turn affects the electrochemical performance of the material. This will be described in the electrochemical performance section.

Fig. 2 Morphology characterization. (a and b) SEM images; (c and d) TEM images; (e) HRTEM image; (f) elemental mapping of Sb₂Se₃/rGO.

The reaction mechanism plays a decisive role in electrochemical performance. Hence, it is vital to explore the reaction mechanism. Sb₂Se₃/rGO is evaluated as an anode material in a half-cell of SIB. Fig. 3a shows CV curves of Sb₂Se₃/rGO during the first three cycles, where the broad cathodic peak centered at 0.98 V is attributed to the intercalation of Na ions into Sb₂Se₃ and the formation of Sb along with Na₂Se.²³ The peak over 0.2–0.7 V is correlated with the alloying reaction between Sb and Na, and the decomposition of electrolyte to form a solid-state interphase (SEI) film.^37–42 The anodic peaks located at 0.75 V and 1.25 V are attributed to the dealloying reaction of Na₃Sb to form Sb, followed by the conversion reaction between Sb and Na₂Se.^43,44 The broad peak around 1.8 V could correspond to the Na ions extracted from Na_xSb₂Se₃ to form Sb₂Se₃.^45,46 The following two cycles are matched well, indicating the excellent reversibility of Sb₂Se₃/rGO during alloying and conversion reactions. To clarify the reactions during sodiation/desodiation processes, ex situ HRTEM images of Sb₂Se₃/rGO were obtained. The ex situ HRTEM images were collected at different discharge/charge voltages in the first cycle. Fig. 3b shows an image of Sb₂Se₃/rGO discharged to 0.7 V. In this image, the lattice fringes of 0.311 nm and 0.241 nm can be attributed to (012) and (220) planes of Sb and Na₂Se, respectively. With the discharge voltage decreased to 0.01 V, the lattice fringes of Na₃Sb appeared (Fig. 3c), indicating the alloying reaction between Na ions and Sb. When fully charged to 2.5 V, the lattice fringes of the sample shown in Fig. 3d suggest that Sb₂Se₃ has formed, indicating the reversibility of the Sb₂Se₃/rGO anode for Na ion storage. All the results agree well with the CV curves in Fig. 3a.

Fig. 3 Electrochemical mechanism analysis. (a) Cyclic voltammograms of Sb₂Se₃/rGO. HRTEM images of Sb₂Se₃/rGO: (b) discharged to 0.7 V; (c) fully discharged to 0.01 V; (d) fully charged to 2.5 V.

The electrochemical properties of precursor (SnSe) and product (Sb₂Se₃/rGO) are shown in Fig. 4. SnSe nanosheets are a precursor material, and the cycle characteristics (Fig. S6, ESI†) and rate performances (Fig. S7, ESI†) were tested. SnSe nanosheets exhibit a capacity of 334 mA h g⁻¹ at a current density of 0.5 A g⁻¹ after 100 cycles. As a material with a nanosheet structure, the rate performance is good because of the fast reaction kinetics. The replacement of Sn by Sb is accompanied by the formation of nanoparticles, the capacity and kinetics being further improved. At the same time, rGO materials are introduced to increase conductivity and cycling stability. Through the structure design, high-rate and excellent low-temperature characteristics can be guaranteed. In order to obtain better electrochemical properties, many conditions have been tested, such as the amount of SbCl₃ added during the reaction (Fig. S8, ESI†), the temperature and time of the hydrothermal reaction (Fig. S9 and S10, ESI†), the calcination temperature in Ar/H₂ (Fig. S11, ESI†), and the cut-off voltage during charge/discharge (Fig. S12, ESI†). After optimization, Sb₂Se₃/rGO with the best electrochemical performance is selected. All of the following examinations are based on optimal conditions.

Fig. 4 Electrochemical performances. (a) Discharge/charge curves of Sb₂Se₃/rGO at a current density of 0.1 A g⁻¹. (b) Cycling performance and (c) rate performance of Sb₂Se₃/rGO. (d) Comparison of results of reported works with ours in terms of capacity retention. (e) Discharge/charge curves of Sb₂Se₃/rGO at different temperatures. (f) The capacity retentions of Sb₂Se₃/rGO along with temperature variations between 25 and −15 °C at a various current densities of 0.2, 0.5, 1, and 2 A g⁻¹.

Fig. 4a shows the galvanostatic charge/discharge curves for the first three cycles. The cathodic/anodic peaks in CV curves match well with the charge/discharge plateaus. As we can see from the first-cycle charge/discharge curve, the initial Coulombic efficiency is ∼67.3%. The capacity loss comes from the decomposition of electrolytes, the formation of SEI film, and so on.^47,48 In the following cycles, the capacity is almost unchanged, indicating the good reversibility of the compound. Fig. 4b shows the cycling performance of Sb₂Se₃/rGO within 0.01–2.5 V at a current density of 0.5 A g⁻¹. It indicates that the composite exhibits a reversible capacity at 511 mAh g⁻¹ after 50 cycles. As shown in Fig. S13 (ESI†), the capacity of rGO is about 75 mA h g⁻¹ at a current density of 0.5 A g⁻¹. The theoretical specific capacity of Sb₂Se₃/rGO composite is 75 mA h g⁻¹*19% + 670 mAh g⁻¹ × 81% = 557 mA h g⁻¹, which is consistent with the results in Fig. 4b. The excellent rate performance is shown in Fig. 4c. The capacity of Sb₂Se₃/rGO is 580.6 mA h g⁻¹ at 0.1 A g⁻¹, 547 mA h g⁻¹ at 0.2 A g⁻¹, 517.5 mA h g⁻¹ at 0.5 A g⁻¹, 498.8 mA h g⁻¹ at 1 A g⁻¹, 467.9 mA h g⁻¹ at 2 A g⁻¹, 396.8 mA h g⁻¹ at 5 A g⁻¹, and 311 mA h g⁻¹ at 10 A g⁻¹. Even at a high current density of 20 A g⁻¹, it still has a capacity of 266.5 mA h g⁻¹ with a capacity retention of 46% related to the discharge capacity at 0.1 A g⁻¹. This is in good agreement with the large surface area and multiple active sites of small Sb₂Se₃ nanoparticles, which accelerate Na ion diffusion kinetics.⁴⁹ It is found that the rate performance of Sb₂Se₃/rGO is superior to that of previously reported Sb₂Se₃ in SIBs (Fig. 4d), including polypyrrole-coated Sb₂Se₃ microclips (486 mA h g⁻¹ at 2 A g⁻¹),²⁰ Sb₂Se₃ nanowires (247 mA h g⁻¹ at 2 A g⁻¹),²³ capsular carbon shell-encapsulated Sb₂Se₃ (398.7 mA h g⁻¹ at 2 A g⁻¹),²⁴ and carbon nanofibers with embedded Sb₂Se₃ nanoparticles (250 mA h g⁻¹ at 10 A g⁻¹).²⁶ To understand the excellent electrochemical performances of Sb₂Se₃/rGO in SIBs, EIS was measured at open circuit potential (OCP) and 2.5 V after five cycles (Fig. S13, ESI†). It is fitted by an equivalent circuit (Table S1, ESI†). Sb₂Se₃/rGO presents a smaller charge-transfer resistance (R_ct) after five cycles. The result is associated with the faster interface kinetics, resulting in excellent rate performance.⁵⁰ However, R_ct after 100 cycles is greater than after 5 cycles, because of the continuous thickening of the SEI film and the agglomeration caused by the structural destruction of Sb₂Se₃, causing a slowed ion conduction. In addition to the excellent rate performance, the composite also displays outstanding LT performance. Fig. 4e shows the discharge curves tested under various temperatures from 25 °C to −15 °C at a current density of 0.1 A g⁻¹. With a drop in temperature, the capacity gradually decreases. This can be associated with the difficult sodiation and serious polarization of the electrode at LT.⁵¹ The discharge curves also show an increase in polarization voltage. The main reason is the slow desolvation of Na⁺ ions and the slow transport of Na⁺ ions in the electrode material. The LT performance of SnSe was also tested (Fig. S14, ESI†). Fig. 4f shows the capacity retentions at different discharge current densities (0.1, 0.2, 0.5, 1, and 2 A g⁻¹) and testing temperatures (from 25 °C to −15 °C). The capacity retention at −15 °C compared to that at 25 °C is ∼77.5% at 0.2 A g⁻¹ and ∼43% at 2 A g⁻¹. This result is better than that of SnSe tested at the same condition (Fig. S15, ESI†), proving the importance of our structural design.

Conclusions

In summary, Sb₂Se₃/rGO is synthesized by the precipitation transformation method with controllable shape and size. This composite exhibits an outstanding rate performance owing to small Sb₂Se₃ nanoparticles with an increase of specific surface area and increase of active sites. The diffusion and storage of sodium ions become more rapid, resulting in good rate performance. What is more, rGO can alleviate the particle agglomeration caused by volume expansion of Sb₂Se₃ and increase the conductivity of the compound. This synthesis strategy can tightly bind Sb₂Se₃ nanoparticles to rGO, and achieve fast conduction of ions and electrons simultaneously. As for the rate capability, the composite exhibits a reversible capacity of 266 mAh g⁻¹ at 20 A g⁻¹. Even at −15 °C, the capacity retention remains at 38% at a current density of 2 A g⁻¹. All those data indicate that this composite structure has promising potential in low-temperature SIBs. In the future, the precipitation transformation conversion method could be widely used in the synthesis of other composite nanomaterials.

Author contributions

Lulu Hu: methodology, formal analysis, investigation, writing – original draft, resources. Jun Pan: conceptualization, investigation, data curation, writing – original draft, writing – review & editing, supervision. Pei Zhao: draft curation, supervision. Gejun Shi: data curation, supervision. Baofeng Wang: investigation, funding acquisition, resources, writing – review & editing. Fuqiang Huang: methodology, writing – review & editing, supervision, project administration, funding acquisition.

Conflicts of interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This work is financially supported by the National Natural Science Foundation of China (No. 22075173), the Science and Technology Commission of Shanghai Municipality (No. 19DZ2271100 and 21010501100), the Key Research Program of Frontier Science of the Chinese Academy of Sciences (Grant No. QYZDJ-SSW-JSC013), and the Super Post-Doctoral Fellow Program of Shanghai (E01SCB17).

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Footnote

† Electronic supplementary information (ESI) available. See DOI: 10.1039/d2ma00170e

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