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Graphene-Loaded Bi2Se3: A Conversion-Alloying Type Anode Material for Ultrafast Gravimetric and Volumetric Na-Storage Dan Li, Jisheng Zhou, Xiaohong Chen, and Huaihe Song ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b09538 • Publication Date (Web): 16 Aug 2018 Downloaded from http://pubs.acs.org on August 19, 2018

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ACS Applied Materials & Interfaces

Graphene-Loaded Bi2Se3: A Conversion-Alloying Type Anode Material for Ultrafast Gravimetric and Volumetric Na-Storage Dan Li, Jisheng Zhou*, Xiaohong Chen* and Huaihe Song State Key Laboratory of Chemical Resource Engineering, Beijing Key Laboratory of Electrochemical Process and Technology for Materials, Beijing University of Chemical Technology, Beijing, 100029, P. R. China. *E-mail: [email protected]; [email protected] ABSTRACT: Sodium ion battery (SIB) has been a promising alternative for sustainable electrochemical energy-storage devices. However, it still needs great efforts to develop electrode materials with ultrafast gravimetric and volumetric Na-storage performance, due to difficult balance between Na-ion diffusion kinetics and pressing density of materials. In this work, Bi2Se3/graphene composites, synthesized by a selenization reaction, are investigated as anode materials for SIBs. Na-ion storage mechanism of Bi2Se3 should be attributed to a combined conversion-alloying one by a series of ex-situ measurements. In the composites, Bi2Se3 particles with an average diameter of 100 nm are uniformly dispersed onto graphene with strong interfacial interaction. Despite of their nanoscale size, the pressing density of Bi2Se3/graphene composite could still reach a high value of 2.07 g/cm3. Therefore, the 1

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composites can deliver a high gravimetric specific capacity of 346 mAh/g and volumetric specific capacity of 716 mAh/cm3 at a current density of 0.1 A/g. Remarkably, the composites exhibit an ultrafast Na-storage capability and a negligible capacity fading with the increasing of current density from 0.2 to 5 A/g. Even at 10 A/g (≈30 C), the composites still possess a gravimetric capacity of 183 mAh/g and volumetric capacity of 379 mAh/cm3 with ultra-stable cyclability up to 1000 cycles. This work introduces a valid route to design electrode materials with both excellent gravimetric and volumetric performance of Na-ion storage. KEYWORDS: Bismuth selenide, Graphene, Sodium-ion battery, Gravimetric capacity, Volumetric capacity

INTRODUCTION

Sodium ion batteries (SIBs) have aroused a revived interest in the energy storage filed due to great natural plenitude and even distribution of Na reserves.1-5 However, the repeated volume expansion/contraction and slow Na-ion transport dynamics in the host materials, caused by the large radius of Na-ion, limit the breakthrough of SIBs in practical application.611

Therefore, great efforts have been devoted to develop promising Na-ion storage materials,3-

11,12

novel electrolytes13,14,15 and even new type of binders.16 For example, Gao et al.16

developed a polymer network binder for anode materials by a facile cross-linking chemistry, and found that the designed polymer binder could effectively accommodate the large volume variation of the anode materials during sodiation/desodiation processes. However, the choice of suitable electrode materials remains one of the main problems hindering the commercialization of SIBs. Among various electrode materials, bismuth and bismuth 2


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chalcogenides (Bi2X3, X=O or S) have attracted great attentions as the promising anode materials for SIBs.17-26 The Na-storage mechanism of metallic bismuth can be attributed to an alloying reaction. Very recently, Wang and co-workers reported that Bi nanoparticles intercalated in graphite exhibited an excellent rate performance.20 However, the specific capacity of metallic Bi can only be maintained at ca. 110-160 mAh/g at a higher current density of over 1 A/g.17-20 Compared with metallic Bi, bismuth chalcogenides are expected to possess a higher capacity because an additional capacity contribution is provided from a conversion reaction (expressed as: Bi2X3 + 6Na ↔ 2Bi + 3Na2X) besides from alloying capability of Bi.22-26 For instance, the pristine Bi2O3 reported by Nithya22 exhibited a reversible specific capacity of 600 mAh/g as anode materials for SIBs. Rod-like Bi2S3 synthesized by Jiang and Dou et al.23 can also deliver a high capacity of 658 mAh/g. Nevertheless, oxide and sulfide of bismuth show inferior rate capability and rapid attenuation of capacity due to their poor electrical conductivity, limited space structures, and enormous volume variation caused by repeated sodiation/desodiation process. Compared with oxide and sulfide, selenide of bismuth owns higher electrical conductivity and larger crystal lattice. Therefore, it is expected that bismuth selenide can exhibit more promising Na-ion storage performances than bismuth oxide or sulfide.3,27,28 From the viewpoint of high volumetric Na-ion storage performance, bismuth selenide should also be one of the important candidate materials. Except for the gravimetric Nastorage performance, volumetric Na-storage performance should also become one of the most important evaluation for electrode materials with the trend of miniaturization, lightweight and integration for design of electric cars and other electronics.27-29 However, it still need great efforts to design electrode materials with both ultrafast gravimetric and volumetric Na-ion storage properties, due to difficult balance between Na-ion diffusion kinetics and pressing 3



density of material. Recently, it was reported that some anode materials such as Sn, SnSb, Sb, P, Sn4P3, SnP3, etc., can deliver higher theoretical volumetric capacities for Na-ion storage.30,31 Unfortunately, their practical volumetric capacities are few evaluated. Up to now, volumetric capacities of only several metal chalcogenides are investigated. For example, the SnTe/C composite materials reported by Park et al.32 can show a volumetric capacity of 639 mAh/cm3 at 50 mA/g. In addition, MoS2/carbon nanotubes film electrode reported by Li et al.33 can deliver a volumetric capacity of ca. 650 mAh/cm3. One of the main reasons for higher volumetric capacity of transitional metal chalcogenides should be attributed to their higher theoretical density (6.44 g/cm3 for SnTe, 4.80 g/cm3 for MoS2). Hence, after compositing with carbon, a higher tap density or pressing density for composites can still be maintained (1—2 g/cm3),29,32,33 which is comparable to the pressing density of commercial graphite or silicon electrode in the lithium-ion batteries.34-36 Compared with these transitional metal chalcogenides, bismuth selenide owns a higher density of 7.47 g/cm3.37 Therefore, it is expected that bismuth selenide can also exhibit an excellent volumetric Na-ion storage performance. Herein, the composite of Bi2Se3/graphene nanosheets (GNS) is designed by a selenization reaction to achieve high-performance Na-ion storage (Scheme 1). In the composite, Bi2Se3 particles with an average diameter of 100 nm are uniformly dispersed onto GNSs with strongly interfacial interaction. The pressing density of Bi2Se3/GNS composite could reach a high value of 2.07 g/cm3. Bi2Se3, as one of the typical metal selenides, has showed enormous attractive advantages as an electrode material in the field of energy storage including lithiumion storage,38,39 solar cell40 and supercapacitors.41 However, as far as we know, there is only one report about the Bi2Se3 as anode material for SIBs, which shows interesting Na-ion storage properties.37 However, achieving the excellent Na-ion storage performance of Bi2Se3 4


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including ultrafast gravimetric/volumetric Na-storage performances and a long cycle life at high rates remains a great challenge. The gravimetric and volumetric Na-storage properties of Bi2Se3/GNS composites are investigated, and their Na-ion storage mechanism should be attributed to a combined conversion-alloying reaction. The Bi2Se3/GNS composite can achieve both high reversible gravimetric capacity of 346 mAh/g and volumetric capacity of 716 mAh/cm3 at 0.1 A/g. Remarkably, it shows an excellent high-rate capability and a negligible capacity fading with the increasing of current density from 0.2 to 5 A/g (≈ 15 C). Even at 10 A/g (≈ 30 C), ultra-stable gravimetric capacity of 183 mAh/g and volumetric capacity of 379 mAh/cm3 can be realized after 1000 cycles. EXPERIMENTAL SECTION Synthesis of samples Scheme 1. Schematic illustration for the synthetic procedure of the Bi2Se3/GNS composite.

As shown in Scheme 1, the Bi2Se3/GNS composites were prepared by a facile selenization reaction using Bi/GNS as precursors. The typical synthesis process is as following: first, 202 mg of Bi(NO3)3·5H2O and 40 mg of graphene were sonicated in 40 mL of alcohol for 1 h with ultrasonic treatment to obtain a homogeneous dispersion liquid. Then the dispersion 5



liquid was heated at 75 oC to obtain the Bi(NO3)3/GNS composite by vaporing the alcohol. Subsequently, the Bi(NO3)3/GNS was reduced to obtain the Bi/GNS composite in the NaBH4 solution under the ice-bath condition. At last, the Bi/GNS was converted to Bi2Se3/GNS composite by selenization in a quartz-tube oven. In the selenization process, 0.050 g of Bi/GNS and 0.6 g of Se powders were laid flat in the covered crucible, and then annealed at 400 oC for 12h in a flowing Ar gas with 15% H2. For comparison, pure Bi2Se3 without graphene was also synthesized by the same way as the Bi2Se3/GNS composite. Structural and physical characterization The crystal structure of the samples were measured by X-ray diffraction (XRD, Rigaku D/max-2500B2+/PC using Cu Kα radtation). The mass content of Bi2Se3 in the composite was evaluated by the Thermogravimetric analysis (TGA, STA449C). The elements’ chemical states of the samples were measured by the X-ray photoelectron energy spectra (XPS, monochromated Al Kα X-ray source with 30 eV pass energy). The specific surface areas of Bi2Se3/GNS composite and pure Bi2Se3 was tested by the Nitrogen adsorption–desorption measurements (Micromeritics ASAP2046). The morphology and microstructure of the obtained samples were characterized by scanning electron microscopy (SEM, ZEISS SUPRATM 55), high-angle annular dark-field scanning transmission electron microscopy (HAADF-TEM, TECNAI G2 F30), and Elemental dispersive spectroscopy (EDS) mapping (TECNAI G2 F30). The detailed measurement parameters and conditions can be seen in our previous works.3,42 Electrochemical characterization 6


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The Na-ion storage performances of obtained samples were characterized using coin cells of CR2025 type at room temperature. The cells were assembled in the glove box filled with Ar. We employed the pure Na foils as the counter electrodes, glass fibers as separators, and one molar NaSO3CF3 solution in diglyme as electrolyte. The preparation of tested electrodes was completed through three-step procedures. First, slurry was obtained by mixing binder (sodium carboxymethylcellulose, CMC), conductive additive (super P) and active material with a mass ration of 1: 1: 8 using distilled water as solvent. Then, the slurry was coated on the current collector of Cu foil. At last, the Cu foil coated with the slurry was dried at the temperature of 120 oC for 12 h under the vacuum condition. The mass of active materials for each electrode can be controlled at ca. 1.13 mg/cm2. The discharge/charge tests were carried out using a Land battery tester (CT2001A, China) under a voltage range from 0.5 to 2.9 V. Electrochemical impedance spectral (EIS) tests were performed on the electrochemical workstation (CHI 660E) using a frequency range from 100 kHz to 10 mHz, and cyclic voltammetry (CV) measurements were also carried out on the electrochemical workstation using various scanning rates from 0.1 to 2 mV/s. RESULTS AND DISCUSSION

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Figure 1. XRD patterns of the obtained Bi2Se3/GNS composite and pure Bi2Se3. In Figure 1, all the peaks in the XRD pattern of Bi2Se3/GNS composite match well with Bi2Se3 (JCPDS: 33-0214), and there are no other diffraction peaks of impurities, indicating the successful synthesis of Bi2Se3/GNS. In the low-magnification SEM image (Figure 2a), a curled morphology and wrinkled structure of the composite can be clearly observed. After further amplification (Figure 2b), Bi2Se3 particles uniformly anchored on the graphene can be distinguished obviously. According to the TGA analysis (Figure S1), the mass content of Bi2Se3 in the Bi2Se3/GNS composite is estimated to be 83.9 wt% (Detailed calculation process can be seen in the Supporting Information). The TEM image (Figure 2c) shows in further that the Bi2Se3 particles are evenly dispersed onto graphene, which is agreement with SEM image. Through particle size distribution, average diameter size of Bi2Se3 particles is ca. 100 nm. The HRTEM image (Figure 2d) taken from the edge area of one of the Bi2Se3 particles indicates a lattice spacing of 3.04 Å, which belongs to (015) plane of Bi2Se3. Elemental mapping images (Figure 2e (i-iv)) obviously reveal a homogeneous spatial distribution and uniform growth of Bi2Se3 particles on the GNS surfaces. However, the bare 8


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Bi2Se3 particles without the graphene tend to aggregate by attaching with each other to form microscale particles with ca. 4 μm diameter (Figure S2). The XRD pattern of pure Bi2Se3 particles exhibits the higher intensity compared with that of Bi2Se3/GNS, which is also an indicative of larger particle size of pure Bi2Se3 particles. N2 adsorption–desorption tests (Figure S3) reveal that the specific surface area of the pure Bi2Se3 particles (7.6 m2/g) is lower than that of Bi2Se3/GNS (28.2 m2/g), which should be ascribed to the addition of graphene and smaller size of Bi2Se3 particle in the Bi2Se3/GNS composite.29

Figure 2. The morphology and structure measurements for Bi2Se3/GNS composite: SEM images of obtained Bi2Se3/GNS composite at the (a) low and (b) high magnification; (c) TEM images of Bi2Se3/GNS and the corresponding diameter statistic of Bi2Se3 nanoparticles in the inset figure; (d) HRTEM image of a Bi2Se3 nanoparticle loaded on the GNS; and (e) Elemental distribution of the Bi2Se3/GNS composite: (i) HAADF-TEM image and the corresponding mapping images of (ii) C, (iii) Bi and (iv) Se elements.

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Elemental chemical states of Bi2Se3/GNS composite were investigated in further by the XPS test. The XPS survey spectrum reveals that Bi, Se, C, and O four elements are present in the composite (Figure 3a). In the Figure 3b, the C 1s spectrum of the Bi2Se3/GNS composite can be fitted to three peaks at the 284.9, 286.5 and 289.4 eV, which are corresponding to the C (C=C/C−C) in aromatic rings, C−O and O−C=O functional groups, respectively.43,44 In the Bi4f spectrum (Figure 3c), two peaks presented at 157.5 and 162.9 eV should be attributed to Bi 4f7/2 and Bi 4f5/2 of Bi2Se3,45,46 respectively. The valence state of Bi in the compound Bi2Se3 should be Bi3+, while the valence state of Se should be Se2-.47,48 In addition, the other two peaks at 158.8 and 164.4 eV should be ascribed to Bi 4f7/2 and Bi 4f5/2 of oxide on the surface of Bi2Se3.26 The Se 3d spectrum of Bi2Se3/GNS composite in Figure S4 shows two peaks located at 52.7 eV (Se 3d5/2) and 53.7 eV (Se 3d3/2), which should also correspond to Bi2Se3.49,50 Noticeably, the O 1s spectra effectively imply that there exists a strong interfacial interaction between GNS and Bi2Se3 (Figure 3d). In the O1s spectrum of original GNS, there are two peaks at 533.2 and 531.7 eV, which should be ascribed to C-O and C=O groups.51-53 In the O 1s spectrum of the composites, besides the peak from C-O group, there are other two peaks located at 530.5 and 532.0 eV, respectively. The peak at 530.5 eV should be ascribed to the surface bismuth oxide, while the one at 532.0 eV can be assigned to C-O-Bi.24 The presence of C-O-Bi indicates the strongly interfacial interaction between Bi2Se3 and graphene matrix. Such an oxygen-bridged interface could not only be helpful to the ion and electron’s transmission between the Bi2Se3 and graphene matrix, but also effectively prevent the exfoliation of Bi2Se3 particles from the graphene surfaces during the discharge/charge processes.42,54-55

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Figure 3. Elemental chemical states: (a) XPS survey spectrum of Bi2Se3/GNS, and its (b) C 1s and (c) Bi 4f spectra; (d) O 1s spectra of original GNS and Bi2Se3/GNS. The Na-storage properties of the Bi2Se3/GNS and pure Bi2Se3 are tested using CR2025 type coin cells. Figure 4a exhibits the initial five CV curves of the Bi2Se3/GNS composites at a scanning rate of 0.1 mV/s. In the first scan curve, there are two reduction peaks at approximately 1.10/0.65 V and four oxidation peaks at approximately 0.77/1.50/1.66/1.82 V, indicating multi-steps sodiation/desodiation reactions. Due to the irreversible generation of solid electrolyte interphase (SEI) films, the first scan is distinguishable from subsequent cycles. It can be seen that the CV peaks become weak after the initial three cycles and overlap after the 4th and 5th cycle, which should be corresponding to the activationstabilization processes of the Bi2Se3/GNS anode experienced during the discharge-charge cycles.56,57 Figure 4b shows the voltage-capacity curves of Bi2Se3/GNS at the current density of 0.1 A/g, and the discharge/charge voltage plateaus are in great accord with the CV peaks.

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Figure 4. (a) Initial five CV curves of Bi2Se3/GNS electrode at a scan rate of 0.1 mV/s in potential range from 0.5 to 2.9 V; (b) The discharge-charge curves for Bi2Se3/GNS at 0.1 A/g; and (c) Na-ion storage mechanism investigation by the ex situ XRD patterns of the Bi2Se3/GNS electrode recorded at different potentials as marked in the initial discharge/charge process: A) electrode without discharge/charge, B) discharging to 1.25 V, C) discharging to 1.2 V, D) discharging to 1.0 V, E) discharging to 0.65 V, F) discharging to 0.5 V, G) charging to 0.75 V, H) charging to 1.0 V, I) after the first complete cycle. 12


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The possible Na-storage mechanism for Bi2Se3/GNS was investigated in further by ex-situ XRD, SAED, HRTEM and XPS analyses at different discharge/charge potentials (Figure 4c, 5, and S5). For the XRD pattern of pristine Bi2Se3/GNS electrode (Stage A), sharp peaks at 2θ ≈ 25.0, 29.4, and 40.3o corresponding to Bi2Se3 (JCPDS: 33-0214) can be clearly distinguished. After discharging to 1.25 V (Stage B), the electrode still remains the original structure without presence of any new peaks. When the voltage is discharged to 1.2 V (Stage C), diffraction peaks of NaBiSe2 and metallic Bi appear, and peaks belonging to Bi2Se3 markedly diminish. SAED, HRTEM and XPS tests also confirm the appearance of NaBiSe2 and metallic Bi (Figure 5b, g and S5). These results imply that the conversion reaction between Bi2Se3 and Na ions happens. When the voltage is gradually discharged to 1 V (Stage D) and 0.65 V (Stage E), diffraction peaks of metallic Bi are obviously enhanced, indicating that the NaBiSe2 is converted in further to Na2Se and metallic Bi via the conversion reaction. At the stage E, diffraction peak of Na2Se can also be distinguished. When the voltage is 0.5 V (Stage F), the diffraction peaks of metallic Bi are nearly disappeared, and the peak of NaBi appears. We can also distinguish obviously the diffraction patterns in SAED (Figure 5c), lattices in HRTEM image (Figure 5h), and Bi 4f core-level peak in XPS spectrum (Figure S5) of NaBi. These results indicate that the alloying reaction of metallic Bi with Na ions occurs to generate NaBi in this process.20 In the charge process (Stage G and H), we can only capture the trace of metallic Bi through XRD, SAED and HRTEM (Figure 5d and i), so it should be corresponding to the dealloying process of NaBi.20 Dealloying process of NaBi is also confirmed by the Bi4f XPS spectrum (Figure S5), because the core-level peaks of metallic Bi reappear. Finally, after a complete cycle (Stage I), the weak peak assigned to NaBiSe2 reappears, and the crystal lattice fringes and patterns assigned to NaBiSe2 phase could also be observed in HRTEM and SAED 13



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(Figure 5e and j), which means that Bi gradually reacts with Na2Se to generate NaBiSe2. However, the active material cannot be fully reversibly recovered to Bi2Se3 after the first complete cycle: no any characteristic of Bi2Se3 could be distinguished. Furthermore, Bi 4f XPS spectrum after charging to 2.9 V also verifies the reappearance of NaBiSe2 and metallic Bi, and no recovery of Bi2Se3 (Figure S5). Based on above discussion, the possible electrochemical reactions of Bi2Se3/GNS electrode are as follows: Discharge process: 2Bi2 e3 + 3Na+ + 3ea i e2 i

a

Bi + 3NaBi e2 (irreversible)

e-

a e-

i

2 a2 e

(1) (2)

a i

(3)

e-

(4)

Charge process: a i i

i

2 a2 e

a

a i e2

a

e-

(5)

Figure 5. SAED patterns and HRTEM images of the Bi2Se3/GNS electrode collected at various potentials during the first discharge/charge processes: (a, f) electrode without

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discharge/charge, (b, g) discharging to 1.2 V, (c, h) discharging to 0.5 V, (d, i) charging to 1.0 V, (e, j) after the first complete cycle. The first discharge capacity and reversible capacity of Bi2Se3/GNS composite are 365 mAh/g and of 346 mAh/g at 0.1 A/g (Figure 4b), respectively, so the composite shows a high initial Coulombic efficiency of 94.8%. The reversible capacity of graphene obtained after removing Bi2Se3 in the composites is ca. 200 mAh/g (Figure S6). Therefore, it can be calculated that the Bi2Se3 contributes ca. 90.7% of the capacity in the Bi2Se3/GNS. The irreversible capacity should be attributed to the generation of SEI films on the surface of electrode due to the decomposition of electrolyte. For comparison, the reversible capacity of pure Bi2Se3 is 273 mAh/g (Figure S7), which is lower than that of the Bi2Se3/GNS. Figure 6a compares the cyclic stability of pure Bi2Se3 and Bi2Se3/GNS at 100 mA/g. After decay in initial five cycles, the capacity of Bi2Se3/GNS tends to be stable and maintains at 260 mAh/g with a Coulombic efficiency of ca. 100%, whereas the capacity of pure Bi2Se3 drastically decreases to 115 mAh/g after 90 cycles. The rate capabilities of Bi2Se3/GNS and pure Bi2Se3 were evaluated at different current densities from 0.1 to 10 A/g (Figure 6b). Among them, the Bi2Se3/GNS composite shows a superior rate performance compared to pure Bi2Se3. The composite can exhibit a reversible capacity of 346, 243, 236, 229, 222, 212 and 181 mAh/g at 0.1, 0.2, 0.5, 1, 2, 5 and 10 A/g, respectively. When the current returns to 0.1 A/g, the capacity can still maintain the original value, indicating the extraordinary tolerance at high rates. In comparison, pure Bi 2Se3 delivers a capacity of 275, 193, 177, 168, 133, 77 and 44 mAh/g, respectively, from 0.1 to 10 A/g. It can be calculated that the capacity ratio between Bi2Se3/GNS and pure Bi2Se3 increases from ca. 1.2 to 4.1 with the increasing of current density from 0.1 to 10 A/g (Table 15



S1). Noticeably, in our study, Bi2Se3/GNS also exhibits an excellent ultra-long cyclic stability at high rates. With the increasing of current density to 2 and 10 A/g (≈ 6 and 0 C), Bi2Se3/GNS can still possess reversible capacities of 222 and 183 mAh/g with almost no decay after 1000 cycles (Figure 6c), indicating an extraordinary stable Na-ion storage. At present, metallic bismuth and bismuth chalcogenides Bi2X3 (X=O, S and Se) have all been used as anode materials for SIBs.17,19,23,24,26,37 However, the cyclic properties and high-rate capabilities of these materials are still unsatisfactory. For instance, Jiang et al.23 reported that Bi2S3 nanorods can deliver a high capacity of 658 mAh/g at 0.1 A/g, but the capacity fades fast to 320 mAh/g after only 40 cycles. Mai et al.26 reported that heterostructured Bi2S3-Bi2O3 nanosheets can display a reversible capacity of ca. 630 mA h/g at 200 mA/g. However, the capacity drastically falls to ca. 300 mAh/g after only 50 cycles, and its rate capability is also unsatisfactory. Recently, Chen et al.37 also synthesized Bi2Se3/C composites and investigated their Na-ion storage performance. The capacity of Bi2Se3/C composite is higher than that of Bi2Se3/GNS composite here. However, Bi2Se3/GNS composite exhibits the much better rateperformance compared with Bi2Se3/C composite. The Bi2Se3/C composite shows a fast capacity fading with the increasing of current density, and no high-rate cyclic stability measurement was carried out. Hence, comparing with previously reported bismuth-based materials (Figure S9 and Table S2), the Bi2Se3/GNS composite exhibits superior rate capability and cyclic stability as anode materials for SIBs.

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Figure 6. The gravimetric (a) and volumetric (d) cyclic performances of Bi2Se3/GNS and pure Bi2Se3 at 100 mA/g and the corresponding Coulombic efficiencies; The gravimetric (b) and volumetric (e) rate capabilities of Bi2Se3/GNS and pure Bi2Se3 at different current densities from 0.1 to 10 A/g; The gravimetric (c) and volumetric (f) long-term cyclic performances of Bi2Se3/GNS at current densities of 2 and 10 A/g, and the corresponding Coulombic efficiencies; (g) CV curves of Bi2Se3/GNS at various scan rates using the cell after 100 cycles at 0.1 A/g. (h) The linear relationship between log(i) and log(v) at various redox peaks. (i) Capacity contribution ratio of the diffusion and capacitive controlled Na-ion storage processes in the Bi2Se3/GNS at 0.1, 0.2, 0.3, 0.5, 1, and 2 mV/s; (j) Electrochemical impedance plots of Bi2Se3/GNS and pure Bi2Se3 after the third cycle at 0.1 A/g. Except for the gravimetric capacity (Cm, mAh/g), the volumetric capacity (Cv, mAh/cm3) is also one of the important parameters to evaluate the electrochemical performances of materials. The volumetric capacity could be obtained by the following equation:32,33,58

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(6) In the formula, Q stands for the capacity, V is the electrode material’s volume, and ρ is the pressing density of electrode material. The pressing density can be calculated from the loading mass and thickness of electrode materials (Related calculation can be seen in the Table S3).34 In the Figure S10, the thickness of the empty copper foil and copper foil coating with Bi2Se3/GNS and pure Bi2Se3 were measured. By the calculation, the pressing densities ( ) of Bi2Se3/GNS and pure Bi2Se3 electrodes can reach high values of 2.07 and 2.61 g/cm3, respectively. The pure Bi2Se3 and Bi2Se3/GNS can exhibit extremely high volumetric capacities of 712 and 716 mAh/cm3, respectively (Figure 6d). Up to now, there are only a few reports about the volumetric capacity of electrode materials for SIBs such as SnTe/C and MoS2/carbon nanotube composite films.32,33 It is obvious to see that the volumetric capacity of Bi2Se3/GNS composite is comparable to those of reported materials. For instance, Li et al.33 reported that MoS2/carbon nanotube composite films with a density of 1.7 g/cm3 can exhibit a volumetric capacity of 600 mAh/cm3. However, no rate volumetric capacity and cyclic stability at high current densities for these reported materials were evaluated.32,33 Noticeably, the Bi2Se3/GNS electrode also shows excellent volumetric capacity at higher current densities. Only 13% capacity fading occurs with the increasing of current density from 0.2 to 5 A/g, which is obviously better than that for pure Bi2Se3, (Figure 6e and Table S1). Especially, at ultrafast current densities of 2 and 10 A/g, Bi2Se3/GNS composite still shows relatively high and ultra-stable volumetric capacity of 460 and 379 mAh/cm3 after 1000 cycles (Figure 6f). Therefore, the Bi2Se3/GNS composite with both ultrafast, stable gravimetric and volumetric capacity will be more competitive and desirable in design of simple and portable electronic products.

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In order to clarify the possible reasons for ultrafast gravimetric and volumetric electrochemical performances of the composites, the Na-storage kinetics of Bi2Se3/GNS are investigated by CV analysis at various scanning rates from 0.1 to 2 mV/s (Figure 6g). As the scanning rate increasing, the intensities of the current density shows a linear relationship with the square root of the scanning rate, implying that there are both non-Faradaic and Faradaic electrochemical processes in the sodiation/desodiation processes.59-61 There exists the linear relationship between log (i) and log (v) plots for every redox peak (Figure 6h). The values of b in the five CV peaks are calculated to be 0.80, 0.83, 0.96, 0.67 and 0.95. Except for the peak 4, the values for other four peaks are close to 1, indicating that the Na-ion storage processes are dominantly controlled by the pseudocapacitive behaviour. Furthermore, to provide insights and quantify the total capacitive contribution in the material, the capacitive and diffusion contributions are separated at a fixed voltage in terms of following equation: (7) Where

and

stand for the diffusion and capacitive contributions, respectively.60

The capacity contribution coming from the diffusion- and capacitance-controlled processes at different scanning rates are shown in Figure 6i. The capacity contribution from capacitancecontrolled process is improved gradually with the increasing of scanning rate. At a high scanning rate of 2 mV/s, the capacity contribution from capacitance-controlled process is as high as 97.5%. Besides, the strong oxygen bridges of the C-O-Bi bond between Bi2Se3 and the GNS ensure an efficient electron pathway upon sodiation/desodiation. By simulation of the EIS spectra, the charge transfer resistance Rct (4.2 Ω) of i2Se3/GNS is obviously lower than that (7.1 Ω) of pure

i2Se3 (Figure 6j and Table S4), suggesting the highly improved electronic 19



transfer network in the composites. Furthermore, the morphology and bonding states of the Bi2Se3/GNS electrode after electrochemical processes were further investigated via TEM and XPS (Figure S11). TEM images show that Bi2Se3 nanoparticles in the composite are still evenly anchored on the surface of graphene after cycling (Figure S11 a and b). XPS analysis reveals that the oxygen-bridge (C-O-Bi) bonds between graphene and Bi2Se3 are still existed (Figure S11 c). This is an indicative of the stable interfacial connection between Bi2Se3 and GNS during the cycling, which is helpful to the smooth electron transfer. Therefore, capacitance-controlled electrochemical process and strong interfacial interaction are the favourable factors for Na-ion storage dynamics to support high-rate performances of Bi2Se3/GNS composites. CONCLUSION In summary, Bi2Se3/GNS composites are synthesized by the selenization reaction. Their gravimetric and volumetric Na-storage performances are investigated in detail. Na-ion storage mechanism of Bi2Se3 can be ascribed to a combined conversion-alloying reaction. The Bi2Se3/GNS composite can deliver a high gravimetric specific capacity of 346 mAh/g and volumetric specific capacity of 716 mAh/cm3 at 100 mA/g. Remarkably, the composite possesses a superior high rate Na-ion storage and nearly no decrease occurs of capacity with the increasing of current density from 0.2 to 5 A/g. Even at 10 A/g (≈ 0 C), a high reversible gravimetric capacity of 183 mAh/g and volumetric capacity of 379 mAh/cm3 can be obtained without obvious decay after 1000 cycles. Ultrafast gravimetric and volumetric electrochemical performances should be ascribed to capacitance-controlled Na-ion storage process and strongly interfacial interaction, which are the favourable factors of Na-ion storage dynamics to support high-rate Na-storage of Bi2Se3/GNS composites. Accordingly, 20


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the Bi2Se3/GNS composite offers remarkable application potential toward practical applications in SIBs. ASSOCIATED CONTENT Supporting Information. The TG curve, N2 adsorption–desorption isotherm and the Se 3d spectrum of Bi2Se3/GNS composite. SEM images, N2 adsorption–desorption isotherm and discharge-charge curves of pure Bi2Se3. The SEM images, XRD patterns, TG curves and electrochemical performances of Bi2Se3/GNS composites with various raw material ratio (C: Bi=4, 8, 12). The Bi 4f spectra of Bi2Se3/GNS electrode collected at various potentials. The electrochemical performance of GNS at a low current density of 0.1 A/g. TEM images with low and high magnification and O 1s spectrum of Bi2Se3/GNS electrode after 2 cycles at 0.1 A/g. Cross-section SEM images of electrodes. The main experimental parameters of prepared electrodes. Randles equivalent circuit and the dynamical parameters of Bi2Se3/GNS and pure Bi2Se3. Specific capacity ratio of the Bi2Se3/GNS to pure Bi2Se3. Comparison of capacity retention of bismuth-based anodes. This material is available free of charge via the Internet at http://pubs.acs.org. AUTHOR INFORMATION Corresponding Author * Email: [email protected] (J Zhou), [email protected] (X Chen) Notes The authors declare no competing financial interest. ACKNOWLEDGMENT

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