Accepted Article

Title: Flower-like VS4/rGO Composite: an Energy Storage Material for

Aluminum-ion Battery

Authors: Shuqiang Jiao

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To be cited as: ChemSusChem 10.1002/cssc.201702270

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ChemSusChem 10.1002/cssc.201702270

Flower-like VS4/rGO Composite: an Energy Storage Material for

Aluminum-ion Battery

Xuefeng Zhang, Shuai Wang, Jiguo Tu, Guohua Zhang,* Shijie Li, Donghua Tian and

Shuqiang Jiao*

Accepted Manuscript
State Key Laboratory of Advanced Metallurgy, University of Science and Technology Beijing,

Beijing, 100083, P R China. *Corresponding Authors: E-mail: sjiao@ustb.edu.cn (S Jiao),

ghzhang_ustb@163.com (G Zhang)

Abstract

The flower-like VS4/rGO (reduced graphene oxide) composite was prepared by a typical

hydrothermal method, which was investigated as cathode for aluminum-ion battery with

non-inflammable and non-explosive ionic liquid electrolytes. The charge/discharge

performance measurements were carried out in a voltage range of 0.1~2.0 V vs. Al/AlCl4-,

which suggests the initial charge/discharge specific capacity approaching 491.57 and 406.94

mA h g-1, respectively, at a current density of 100 mA g-1. Additionally, in the cycling

performance, discharge capacity has been observed to remain over 80, 70 and 60 mA h g-1 at

current densities of 100, 200 and 300 mA g-1 after 100 cycles, respectively. The results of

coulombic efficiency over 90% after 100 cycles and high capacity retained indicate a

favorable cathode material for novel rechargeable aluminum-ion battery.

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ChemSusChem 10.1002/cssc.201702270

Introduction

When lead-acid battery was firstly proposed by Gaston Plante in 1859,[1,2] new secondary

batteries with high energy density and power density along with long cycle life have been

explored in chemical power industry. Since SONY firstly commercialized lithium ion

batteries (LIBs),[3,4] great success has been achieved and dominated battery market has been

Accepted Manuscript
established for portable electronics over the last two decades. However, further development

of LIBs is hindered due to the high cost and insufficient energy density. Therefore,

rechargeable batteries with low-cost, high energy density and long-term cycling stability are

urgently needed to meet the increasing demand for electric vehicles and large-scale energy

storage.

More recently, aluminum-ion batteries (AIBs) have been received intensive interests for

energy storage because aluminum is naturally abundant and cheap compared to lithium.

Aluminum electrode potential is about -1.67 and 2.35 V (vs. SHE)[5] in neutral/acidic and

alkaline medium, respectively. Additionally, the high theoretical volumetric capacity of

aluminum anodes (8040 mA h cm-3) is approximately four times as that of lithium anodes, and

the safety of aluminum allows AIBs as promising safe power sources. However, aluminum

surface is easy to be oxidized in terms of generating inert aluminum oxide films,[6-9] leading to

rapid drop in the aluminum electrode potential. As an amphiprotic metal, aluminum is

chemically active and tends to react with aqueous-medium, which might explain the reason

why industrialization of rechargeable AIBs has not been achieved. According to recent studies

in AIBs, various cathode materials have been explored, such as sulfide materials

(CuS@graphene,[10] Ni2S3@graphene,[11] and Mo6S8[12]) and oxide materials like VO2,[13]

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ChemSusChem 10.1002/cssc.201702270

TiO2,[14] V2O5,[15] graphitic-foam[16-18] and carbon.[19-24] These studies have demonstrated that

aluminum ions can undergo a redox reaction with the positive electrode active materials or as

complex ions intercalate/de-intercalate into/from the electrode materials.

Herein, a novel flower-like VS4/rGO (reduced graphene oxide) composite was

synthesized for AIB cathode. In the AIB operation with a non-inflammable and non-explosive

Accepted Manuscript
ionic liquid electrolyte, electrochemical deposition of Al occurs at the anode and redox

reactions appears at VS4/rGO flower-like composite cathode. The VS4/rGO composite

cathode with a flower-like nano-structure is not only conducive for ion storage, but also can

inhibit volume expansion during charging/discharging process. Meanwhile, good conductivity

and high specific surface area of graphene can effectively improve the charge and discharge

velocity in the VS4/rGO composite. As a result, the fabricated AIB delivers an initial

charge/discharge specific capacities of 491.57 and 406.94 mA g-1, at a current density of 100

mA g-1. Interestingly, the charge and discharge specific capacities exceeded 80 mA h g-1 after

100 cycles with corresponding coulombic efficiency greater than 90%. Additionally, the

specific capacity is over 70 and 60 mA h g-1 at current densities of 200 and 300 mA g-1,

respectively. The high-performance demonstrated that VS4/rGO composite has a great

promising application value in the novel AIBs.

Results and Discussion

Figure 1a shows the formation mechanism of VS4/rGO composite via a typical hydrothermal

method. At the initial stage, the vanadium source (Na3VO4) and sulfur source (CH3CSNH2)

was added into water to form a homogeneous solution. In the subsequent step, the V 4+ and

(S2)2- were gradually chemically bonded on the GO framework due to a large amount of

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ChemSusChem 10.1002/cssc.201702270

oxygen-containing functional groups (-OH, -COOH) on the GO surface.[25] During the

hydrothermal process, VS4 was formed and connected with each other to form a chain

structure. Meanwhile, the GO was transformed into rGO. The as-prepared VS4/rGO were

characterized by XRD (Figure 1b), indicating the good crystallinity of composite. The distinct

diffraction peaks located at 15.76°and 17.01°were indexed to the (011) and (020) planes of

Accepted Manuscript
VS4, respectively. All the diffraction peaks were in good agreement with the standard

spectrum (PDF No. 21-1434). The crystal structure of VS4 has a monoclinic-prismatic

mineral,[26,27] with unit cell parameters a=6.78±0.005 Å, b=10.42 Å and c=12.11 Å, exhibiting

a linear chain structure (Figure 1c).

Atomic force microscopy (AFM) was used to characterize the thickness of VS4/rGO

composite. The AFM image of VS4/rGO composite is shown in Figure 2a and b, which shows

that the thickness of VS4 nanosheets was 13.9 nm. Meanwhile, Figure 2c implies that the

yellow green part is rGO with a thickness of only 3.6 nm. In order to further validate the

as-prepared VS4/rGO composite, the X-ray photo-electron spectroscopy (XPS) measurements

were conducted (Figure 2d and e). As shown in Figure 2d, the XPS peaks of V 2p1/2 and V

2p3/2 located at 523.2 eV and 515.4 eV can be attributed to V 4+ ions.[28] Two distinct peaks at

528.9 eV and 532.5 eV were assigned to O 1s and H2O, respectively,[29-31] which might be due

to the partial reduction of graphene oxide. Another peak appeared at 512.3 eV attributed to V

(vanadium). The S 2p spectrum is shown in Figure 2e, and the binding energy at 164.0 eV

and 165.0 eV were ascribed to S 2p3/2 and S 2p1/2 respectively, which were regarded as

(S2)2-.[32] The XPS results above clearly indicate the successful synthesis of VS4/rGO

composite.

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ChemSusChem 10.1002/cssc.201702270

The morphologies and structures of the VS4/rGO composite were characterized by

scanning electron microscopy (SEM) and transmitting electron microscopy (TEM) (Figure 3).

Figure 3a and b exhibit the SEM images of the flower-like VS4/rGO composite with low and

high magnifications. The VS4/rGO composite displayed some natural flower-like morphology

consisting of numerous petals with the thickness of ~13.9 nm vertically deposited on rGO

Accepted Manuscript
sheets, while some crowded petals are stacked to form a lamellar structure (~3-5 layers),

providing a larger specific surface area. Figure 3c is the representative EDX spectrum,

showing that the element contents of V, S and C were 17.70%, 68.88% and 13.42%,

respectively (Table S1). Moreover, the element content ratio of V to S was 1:3.9, further

confirming the formation of VS4.

In order to further validate the structure of the as-papered VS4/rGO composite cathode,

TEM images with selected area electron diffraction (SAED) are displayed in Figure 4. The

flower-like layered structure in Figure 4a was exactly consistent with the SEM results.

Meanwhile, the corresponding image of SAED exhibited a ring pattern, indicating the

polycrystalline structure of VS4/rGO composite (Figure 4b). Figure 4c shows the

high-resolution TEM (HRTEM) image of the nanosheets, and the rGO was observed on the

edge of VS4 (red line area), suggesting that the rGO sheets serve as the template to induce

VS4 growth (Figure 4d).

In order to demonstrate the structural merits of VS4/rGO in improving cathode

performance, a series of electrochemical measurements were carried out. Cyclic voltammetry

(CV) was used to reveal the electrochemical reaction mechanism of the cathode materials

between 0.1 and 2.0 V versus Al/AlCl4- at a scan rate of 1 mV s-1 (Figure 5a). The CVs of the

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ChemSusChem 10.1002/cssc.201702270

first and second cycles were overlapped very well. During the first cathode oxidation process

of VS4, there were two peaks located at 1.28 V (O) and 1.62 V (O'), while the corresponding

reduction peaks were observed at 0.85 V vs. Al/AlCl4- (R) and 1.03 V (R'), respectively. The

oxidation peaks are from the oxidation of V4+ to V5+and (S2)2- to S2-, while the reduction peaks

were attributed to the reduction of V5+ to V4+ and S2- to (S2)2-. Meanwhile, the CV curves of

Accepted Manuscript
Ta current collector in Figure S1 shows no redox reaction, demonstrating the current collector

was electrochemically inert and not involved in the electrochemical reactions. Figure 5b

shows the charge/discharge curves of the as-prepared pouch battery in the first three cycles

(current density: 100 mA g-1). The AIB delivered an initial discharge capacity of 406.94 mA h

g-1 with a coulomb efficiency of 82.78%, and the irreversible capacity might be attributed to

the decomposition of electrolyte in the low-potential region to form solid electrolyte interface

(SEI) layer.[33-35] Furthermore, there were higher discharge voltage plateaus at 1.03 and 0.85

V. In the first three cycles, the charge/discharge curves of the AIB at higher current densities

of 200 and 300 mA g-1 is shown in Figure S2a and b. The AIB delivered discharge capacities

of 157.57 and 202.95 mA h g-1 at current densities of 200 and 300 mA g-1, respectively.

Meanwhile, the charge/discharge curves exhibited an excellent consistency in voltage plateau.

In order to precisely analyze the cycling performance of the as-papered AIBs, the histogram

of cycling performance from the 10th to 100th cycle (per 10 cycles) is shown in Figure 5c. At a

current density of 100 mA g-1, the discharge capacity of 108 mA h g-1 at the 10th cycle

decreased to 80 mA h g-1 at the 40th cycle, and then stabilized at 93 mA g-1, suggesting that

the AIB maintains a steady state after 40 cycles. Meanwhile, the histogram of cycling

performance at current densities of 200 and 300 mA g-1 at the 10th to 100th cycle was shown in

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ChemSusChem 10.1002/cssc.201702270

Figure S2c and d. Figure 5d shows the cycling performance and coulombic efficiency at a

current density of 100 mA g-1 over 100 cycles. The capacities gradually decreased upon

cycling, and the electrode delivered a reversible capacity over 80 mA h g-1 after 100 cycles

with a coulombic efficiency above 90%. Despite the initial low coulombic efficiency, the

coulombic efficiency of subsequent cycles was much improved, demonstrating a highly

Accepted Manuscript
reversible charge and discharge process which is attributed to the unique flower-like structure.

Moreover, Figure S2e and f show the cycling performance and the coulombic efficiency (200

and 300 mA g-1), as well as demonstrated a good performance.

Figure 6a shows the schematic diagram of charge process of rechargeable Al@VS4/rGO

AIBs using [EMIm]AlxCly ionic liquid electrolyte. The aluminum anode was faced to the

VS4/rGO composite cathode, along with a separator of thickness ~0.675 mm. There were four

rectangles with the colors of black, brown, green and gray, which represents glass fiber

(GF/D), anode (Al), current collector (Ta) and cathode materials (VS4/rGO), respectively

(Figure 6b). Figure 6c clearly displayed the mutual conversion process of charge/discharge in

[EMIm]AlxCly ionic liquid electrolyte.[11,16]

In order to investigate kinetic of electrode process of the AIBs, electrochemical

impedance spectroscopy (EIS) before and after cycling were carried out, and the

corresponding Niquist plots are shown in Figure 7a. All the Niquist plots reflected a depressed

semi-circle at high frequency region, corresponding to the charge transfer process. Meanwhile,

a declined line at the low frequency region corresponds to the Waburg impedance. In high

frequency region, the diameter of the semicircle gradually increased from 10 Ω (10th cycle) to

43 Ω (50th cycle), indicating the growth of SEI film during charging/discharging processes.

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ChemSusChem 10.1002/cssc.201702270

The equivalent circuit model of the AIBs is shown in Figure 7b. Rs represented the internal

resistance of the battery, Rf and CPE1 the resistance and constant phase element of the SEI

film, Rct and CPE2 the charge-transfer resistance and constant phase element of the

electrode/electrolyte interface, and Zw the Warburg impedance. These results were consistent

with the cycle performance analyzed (Figure 5).

Accepted Manuscript
After charging to 2.0 V and discharging to 0.1 V, the V 2p and S 2p XPS spectra of

VS4/rGO composite cathode in Figure 8 are used to analyze the process of redox reactions.

Obviously, the binding energy of V 2p3/2 and V 2p1/2 at 517.4 and 524.5 eV were regarded as

V5+ after discharging to 0.1 V (Figure 8a).[28] Additionally, the binding energy at 530.6, 532.5

and 534.2 eV were assigned to O 1s, O-H and H2O, respectively.[30,31] The V 2p XPS of

VS4/rGO composite cathode after charging to 2.0 V is also shown in Figure 8b. Compared to

the observation at the discharged state, both the binding energy of V 2p1/2 and V 2p3/2 was

shifted by ~0.5 eV indicating that the V5+ was transformed to V4+.[29] Additionally, Figure 8c

shows the detailed scan of S from VS4/rGO composite cathode after being discharged to 0.1 V.

The two peaks at 163.0 eV correspond to S2-.[11,36] The presence of S6+ (168.9 eV) in the

charge and discharge process is possibly due to the oxidation of sulfur in the atmosphere of

electrolyte. After charging to 2.0 V, the binding energy of the peaks represent that the (S22-)

and S6+ moved to 163.0 and 168.4 eV, respectively (Figure 8d). Figure S3a-c show the C 1s

XPS of the VS4/rGO composite, and the binding energy at 288.5 and 285.0 eV were ascribed

to O-C=O bond and C-C bond, respectively. There were almost no changes, but small peaks

appeared at about 286.0 and 286.3 eV after discharging at 0.1 V and charging at 2.0 V,

respectively, indicating that the existence of C-O bonding.[37,38]

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ChemSusChem 10.1002/cssc.201702270

Figure 9a shows the Raman spectra of VS4/rGO composite, and the dominant band at

277 cm-1 was assigned to the vibration mode of V-S stretching,[26] corresponding to the

vibration mode of mono clinic-prismatic mineral VS4. The peak located at 192 cm-1 was

ascribed to the vibration modes of bending (B1).[27]. Figure 9b displays the Raman spectra of

rGO, exhibiting two bands at 1345 cm-1 (D-band) and 1590 cm-1 (G-band), which were due to

Accepted Manuscript
edge planes and disordered structures and the first-order scattering of the E2g mode,

respectively.[39,40] It is noteworthy that the intensity of the D band was comparable to that of

the G band, suggesting the presence of defects. The intensity ratio of D to G bands (ID/IG) was

used to predict the presence of defects within the sample. The intensity ratio of D to G bands

(ID/IG) was 0.597 in the VS4/rGO composite, indicating that the presence of defects in rGO is

attributed to the synthesis of VS4 and rGO as described in Figure 1a. However, the intensity

ratios of D to G bands (ID/IG) were 1.123 and 1.081 in the VS4/rGO composite after charging

to 2.0 V and discharging to 0.1 V, respectively. Obviously, the increased ratio represented the

size reduction of the in-plane sp2 domains, as well as an increase of edge planes and disorder

degree.[39]

Figure 10a and b are AFM images with low and high magnification of VS4/rGO

composite after charging to 2.0 V. The thickness of VS4 was 6.4 nm, which was lower by 7.5

nm compared to that before charging. After being discharging to 0.1 V, the SEM image of

VS4/rGO composite is shown in Figure 10c, which can be found that the flower-like structure

still maintains intact. However, the surface of the petals becomes increasingly rough resulting

in more active sites, which make a contribution to the special capacity during charge and

discharge process. After charging to 2.0 V, the VS4/rGO composite cathode still displayed

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ChemSusChem 10.1002/cssc.201702270

good structural integrity, as shown in Figure 10d.

After discharging, it clearly exhibits the presence of particles (white line area) in Figure

11a. Meanwhile, large amounts of diffraction spots were detected near the rings of diffraction

(Figure 11b) demonstrates that the emergence of a new phase, which may be attributed to the

Al3+ participate in the electrode reaction. After charging, the flower-like structure of VS4/rGO

Accepted Manuscript
was still maintained and the thickness of VS4/rGO composite was thinner than that before

charging (Figure 11c). Additionally, the HRTEM image in Figure 11d also shows the rGO

layers (red line area). Namely, VS4/rGO composite has been well preserved, demonstrating a

good structural stability. The decrease of diffraction spots demonstrates the result of a

polycrystalline structure and almost disappears of new phase (Figure 11e).

Conclusions

In conclusion, a flower-like VS4/rGO composite was synthesized as a cathode material for

AIB. The electrode reaction mechanism in the process of electrochemical and raw material

synthesis was studied. As applied in AIBs, the VS4/rGO composite has obtained a high

electrochemical performance. Initial charge and discharge specific capacity of VS 4/rGO

composite approaches 491.57 and 406.94 mA h g-1 at a current density of 100 mA g-1,

respectively. Therefore, the results highlighted a significant platform to develop

high-performance cathode materials for AIBs.

Experimental Section

The raw materials, Na3VO4 (Aladdin, 99.98%), CH3CSNH2 (Aladdin, 99.0%), deionized

water and alcohol was from Alfa Aesar (Shanghai, China). Graphene oxide was purchased

from XFNANO Co., Ltd (Nanjing, China). The VS4/rGO composite was prepared following

10

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ChemSusChem 10.1002/cssc.201702270

the previous work. The first step, 1.65 g of sodium orthovanadate and 3.37 g of CH 3CSNH2

were added into 120 mL of deionized water with stirring for at least 2 h at room temperature

in order to achieve a homogeneous solution. Subsequently, 30 mg of graphene in 10 mL DI of

water was added into the above homogeneous solution. Then, the obtained suspension was

transferred into a 150 mL autoclave and heated at 160 oC for 24 h. After that, the as-obtained

Accepted Manuscript
powders were washed by deionized water for several times and dried under vacuum at 60 oC

for 12 h.

The preparation of electrolyte (the molar ratio of AlCl3 and 1-ethyl-3-methylimidazolium

chloride ([EMIm]Cl) is 1.3:1) was operated in glove box filled with argon atmosphere

([O2]<0.1 ppm, [H2O]<0.1 ppm). AlCl3 was slowly added and dissolved in the light-yellow

1-ethyl-3-methylimiazolium chloride ([EMIm]Cl) ionic liquid with continuous stirring.

Subsequently, [EMIm]AlxCly ionic liquid electrolyte was maintained at room temperature for

12 h.

The VS4/rGO composite was collected by dispersing the cathode in alcohol with continuous

ultrasonication, and then the collected VS4/rGO composite was placed in an oven at 60 oC for

12 h to evaporate remaining alcohol. Atomic force microscope (AFM, Kratos AXIS Ultra

DLD) was used to analyze the change in the valence of the elements involved in the redox

reaction, XRD (Rigaku, D/max-RB), Raman (190-400, 1000~2000 cm-1), TEM (JEOL,

JEM-2010) and FSTEM with diffraction and SEM with EDX were used to characterize the

structural changes of the VS4/rGO composite after being fully charged at 2.0 V or discharged

at 0.1 V.

Electrochemical testing was performed with pouch cell AIBs. The working electrodes were

11

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ChemSusChem 10.1002/cssc.201702270

prepared by mixing the active material of the VS4/rGO composite (≈100 mg), carbon black

(≈50 mg) and Polyvinylidene Fluoride (PVDF) (≈17 mg) at a mass ratio of 60:30:10 in

magnetic stirrer（Figure S4a）, and then was pasted onto pure tantalum (Ta) foil (0.01 mm, and

length and width: 2 cm × 2 cm, coated active material ~1.5 mg) current collector with an

electrode tab of metallic Mo (Figure S4). Afterword, the as-prepared electrode was dried in an

Accepted Manuscript
oven at 60 oC for 12 h. Moreover, a glass fiber (GF/D) was used as the separator, and anode

was high purity aluminum. The batteries were assembled with Al plastic film in a glove-box

under an argon atmosphere shown in Figure S4. Furthermore, Figure S5 shows the

polarization curves of various metallic and non-metallic current collectors in the

AlCl3/[EMIm]Cl ionic liquid electrolyte system. It can be seen from Figure S5d, when the

potential reached to 2.0 V, the tantalum (Ta) was kept as the base current line, meaning the

possibility as the current collector in the AlCl3/[EMIm]Cl ionic liquid electrolyte system.

Finally, the fully charged batteries in series can light the light emitting diode (LED) lamps as

the practical application (Figure S6). Additionally, the charge/discharge characteristics were

determined by cycling in the voltage range 0.1~2.0 V vs. Al/AlCl4− at different current

densities with a multichannel battery testing system (Neware BTS-53). Cyclic voltammetry

(CV) was performed with CHI 1140C (Shanghai, China) electrochemical workstation with a

scan rate of 0.01 mV s-1 in the voltage range of 0.1~2.0 V. Electrochemical impedance

spectroscopy (EIS) was carried out by CHI 660E in a frequency range of 100 kHz-0.1 Hz at

the 0th cycle, 10th cycle and 50th.

Conflicts of interest

The authors declare no conflict of interest.

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ChemSusChem 10.1002/cssc.201702270

Acknowledgements

This work was supported by the Fundamental Research Funds for the Central Universities

(FRF-TP-17-002C2).

Keywords: sulfide ·cathode ·Al-ion battery

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Accepted Manuscript
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[39] P. Lian, X. Zhu, S. Liang, Z. Li, W. Yang, H. Wang, Electrochim. Acta 2010, 55,

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Lett. 2008, 8, 36-41.

Accepted Manuscript

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ChemSusChem 10.1002/cssc.201702270

Accepted Manuscript
Figure 1. (a) The reaction mechanism of cathode material of VS 4/graphene composite

prepared by hydrothermal synthesis for aluminum-ion battery. (b) XRD pattern of the

as-prepared VS4/graphene composite. (c) The crystal structure diagram of VS4.

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ChemSusChem 10.1002/cssc.201702270

Accepted Manuscript
Figure 2. (a,b) AFM images of original VS4/rGO composite. (c) The thickness of graphene in

the composite. (d,e) The XPS signals of V 2p and S 2p for the original VS4/rGO composite.

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ChemSusChem 10.1002/cssc.201702270

Accepted Manuscript
Figure 3. (a) SEM images of VS4/rGO composite. (b) A partial enlargement of the graph (a).

(c) The representative EDX spectra.

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ChemSusChem 10.1002/cssc.201702270

Accepted Manuscript
Figure 4. (a) TEM image of VS4/rGO composite and (b) A partial enlargement of (a). (c,d)

HRTEM image and corresponding SAED pattern of the original VS4/rGO.

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ChemSusChem 10.1002/cssc.201702270

Accepted Manuscript
Figure 5. (a) CV curves for the first and second cycle. (b) The charge/discharge curves of

VS4/rGO composite cathode at the current density of 100 mA g-1 and the voltage range of

0.1~2.0 V versus Al/AlCl4- from the 1st to 3rd cycle. (c) The histogram of cycling performance

at a current density of 100 mA g-1 from the 10th to 100th cycle (per 10 cycles). (d) The cycling

performance and the corresponding coulombic efficiency at a current density of 100 mA g-1.

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ChemSusChem 10.1002/cssc.201702270

Accepted Manuscript
b
GF/D Al Ta VS4/GO
c
#1
#2
#3

- 3+ - +
AlCl4 Al AlCl3 Al2Cl7 [EMIm]

Figure 6. Schematic diagram of rechargeable Al@VS4/rGO aluminum-ion battery during

charge/discharge process, using the [EMIm]AlxCly ionic liquid electrolyte. The oxidation

reaction occurred between Ultra-valent Al3+ cation and flower-like VS4/rGO composite

cathode during discharge process. On the anode side, 4Al2Cl7- + 3e- → Al + 7AlCl4- during

charge process.

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Accepted Manuscript
Figure 7. (a) The electrochemical impedance spectroscopy (EIS) of aluminum-ion battery at

the 0th, 10th and 50th cycle. (b) The equivalent circuit model of the studied system.

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Figure 8. The V 2p and S 2p XPS signals of the composite cathode after being discharged at

0.1 V (a,c) and charged at 2.0 V (b,d).

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ChemSusChem 10.1002/cssc.201702270

a B1 249 A1 Discharged-0.1 V
b Discharged-0.1 V

D G

ID/IG=1.081
Intensity / a.u.

Intensity / a.u.
Charged-2.0 V D Charged-2.0 V
G

ID/IG=1.123
VS4/graphene G Graphene

Accepted Manuscript
D

ID/IG=0.597
200 250 300 350 400 1000 1250 1500 1750 2000
Raman shift / cm-1 Raman shift / cm-1

Figure 9. (a) Raman spectra of VS4/rGO composite cathode in different states. (b) The

graphene in different states.

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ChemSusChem 10.1002/cssc.201702270

Accepted Manuscript
Figure 10. (a,b) The AFM images of VS4/rGO composite cathode after fully charged at 2.0 V

(over 50 cycles). (c,d) SEM images of the VS4/rGO composite cathode after fully discharged

at 0.1 V and charged at 2.0 V, respectively.

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ChemSusChem 10.1002/cssc.201702270

Accepted Manuscript
Figure 11. (a) TEM images of VS4/rGO composite cathode after fully discharged at 0.1 V. (b)

The corresponding SAED pattern. (c,d) TEM and HRTEM image after fully charged at 2.0 V

(e) the corresponding SAED pattern.

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