Supporting information

Ammonium-Modified Synthesis of Vanadium

Sulfide Nanosheet Assemblies Toward High Sodium

Storage

Bolin Liu,1 Liqin Wang,1 Youqi Zhu,*1 Hui Peng,2 Changliang Du,1 Xinyu Yang,1 Quanqing

Zhao,1 Jianhua Hou,3 Chuanbao Cao*1

1Research Center of Materials Science, Beijing Key Laboratory of Construction Tailorable

Advanced Functional Materials and Green Applications, Beijing Institute of Technology, Beijing

100081, China.

2Analysis and Testing Center, Shandong University of Technology, Zibo 255000, China.

3School of Environmental Science and Engineering, Yangzhou University, Yangzhou 225000,

China.

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*E-mail: yqzhu@bit.edu.cn

cbcao@bit.edu.cn

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Experimental Procedures:
Morphological and Structural Characterizations: The phase information of all the as-synthesized

products was determined by XRD (Bruker D8 ADVANCE diffractometer, Cu Kα). The surface

information including elemental composition and chemical valence was detected by XPS (PHI

Quantera). The microstructure and morphology were observed by TEM (JEM-2100F) equipped

with EDS (EDAX, PW9900), and field emission scanning electron microscopy (FESEM, Hitachi

S-4800). The Raman spectroscopy (Renishaw invia reflex, LabRam HR Evolution) with 633 nm

laser was used to analyze the chemical bonds of these samples.

Electrochemical Measurements: The electrochemical measurements were carried out at room

temperature using CR 2025 coin-type cell. The working electrodes were comprised of active

material, super P and polyvinylidene fluoride (PVDF) in N-Methyl-2-pyrrolidone (NMP) with a

mass ration of 7:2:1. All batteries were assembled in glovebox, where the concentrations of O2 and

H2O were limited below 0.01 ppm. The quality of active materials coated on Cu foil (current

collector) was roughly 1.5 mg with the areal mass loading of 1.0 mg cm−2. The metallic sodium

and Whatman glass fiber were used as the counter electrode and separator, respectively. 1 M NaPF6

in 1,2-dimethoxy-ethane (DME) was used as the electrolyte. The galvanostatic charge and

discharge measurements were performed on Land battery system (LAND CT2001A) at different

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current densities of 0.1 to 5 A g−1 with the voltage range of 0.05-3 V. Cyclic voltammetry (CV)

tests were conducted on electrochemical workstation (CHI 660E, Chenhua) at various sweep

speeds of 0.1 to 2.0 mV s−1. Electrochemical impedance spectroscopy (EIS) was executed on the

same electrochemical workstation with an appropriate AC voltage amplitude of 5 mV

corresponding to frequency range of 105-10−2 Hz.

DFT Calculation method: The present first principle DFT calculations are performed by Vienna

Ab initio Simulation Package (VASP) [1] with the projector augmented wave (PAW) method [2].

The exchange-functional is treated using the generalized gradient approximation (GGA) of

Perdew-Burke-Ernzerhof (PBE) [3] functional. The energy cutoff for the plane wave basis

expansion was set to 450 eV and the force on each atom less than 0.02 eV/Å was set for

convergence criterion of geometry relaxation.15 Å vacuum was added along the z direction in

order to avoid the interaction between periodic structures. The Brillouin zone integration is

performed using 2×2×1 k-point sampling for VS4 (020) or single Γ point for VS4 (110). The self-

consistent calculations apply a convergence energy threshold of 10-5 eV. The DFT-D3 method was

employed to consider the van der Waals interaction [4]. Transition state searching were calculated

using the climbing-image nudged elastic band (CI-NEB) method [5].

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The adsorption energy of Na atom was calculated according to

E𝑎𝑑𝑠 = 𝐸𝑡𝑜𝑡𝑎𝑙 ― 𝐸𝑠𝑢𝑏 ― 𝐸𝑁𝑎

where Etotal is the total energy of the Na adsorbed systems, Esub and ENa are the energies of the

substrate and the Na atom in bulk, respectively.

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Figure S1. FESEM images of VS4 nanosheets.

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Figure S2. (a-c) TEM images, (d) HRTEM image, (e) corresponding SAED pattern, (f) EDS

elemental mapping of VS4-NS.

Figure S3. (a-c) TEM images, (d) HRTEM image, (e) corresponding SAED pattern, (f) EDS

elemental mapping of VS4-NF.

Figure S4. EDS results of VS4-HNS.

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Figure S5. EDS results of VS4-NS.

Figure S6. EDS results of VS4-NF.

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Figure S7. VS4 synthesized with 0 M NH3·H2O (a-c), 3 M NH3·H2O (d-f), 0.01 M pH=12 sodium

hydroxide solution (g-i), 0.01 M pH=12 potassium hydroxide solution (j-l).

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Figure S8. VS4 synthesized with 12 M NH3·H2O.

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Figure S9. VS4 synthesized with 1: 0 M NH3·H2O, 2: 3 M NH3·H2O, 3: 0.01 M pH=12 sodium

hydroxide solution, 4: 0.01 M pH=12 KOH solution and 5: VS4-NS. (a) XRD patterns, (b) Raman

spectra, (c) XPS wide spectra and V 2p (d), S 2p (e) spectra of 1-5.

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Figure S10. VS4 synthesized under 180 oC for 3 min.

Figure S11. VS4 synthesized under 180 oC for 15 min.

Figure S12. (a) N2 adsorption–desorption isotherms and (b) BJH pore size distribution of VS4-NS,

VS4-HNS, VS4-NF.

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Figure S13. VS4 synthesized with 1 mmol V (a-b), 4 mmol V (c-d), 6mmol V (e-f).

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Figure S14. VS4 synthesized with 15 mmol S (a-b), 10 mmol S (c-d).

Figure S15. VS4 synthesized by hydrothermal under 160 oC for 24 h.

Figure S16. XRD patterns of VS4 synthesized by hydrothermal under 160 oC for 24 h.

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Figure S17. VS4 microwave under 180 oC for 5 min then transfer to hydrothermal under 160 oC

for 18h.

Figure S18. VS4-HNS discharge–charge voltage profiles at a current density of 200 mA g−1.

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Figure S19. Electrochemical performances of VS4-NS: (a) discharge–charge voltage profiles at a

current density of 2 A g−1, (b) cycling properties at a current density of 200 mA g−1, (c) rate

capabilities, (d) long-life cycling stability.

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Figure S20. Electrochemical performances of VS4-NF: (a) discharge–charge voltage profiles at a

current density of 2 A g−1, (b) cycling properties at a current density of 200 mA g−1, (c) rate

capabilities, (d) long-life cycling stability.

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Figure S21. Cycling properties at a current density of 2 A g−1 of VS4 synthesized with 0 M

NH3·H2O (a), 3 M NH3·H2O (b), 0.01 M pH=12 NaOH solution (c), 0.01 M pH=12 KOH solution

(d).

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Figure S22. EIS spectra of VS4-NS (a) and VS4-NF (b).

Figure S23. EIS spectra of VS4 nanoparticles.

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Figure S24. Pseudocapacitive contribution (dark red region) at 1.2 mV s−1 of VS4-HNS.

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Figure S25. Electrochemical reaction kinetics of VS4-NS: (a) CV curves under different scan rates,

(b) linear relation between log (scan rate) and log (peak current), (c) capacitive contribution ratios,

and (d) pseudocapacitive contribution (dark red region) at 1.0 mV s−1.

Figure S26. Electrochemical reaction kinetics of VS4-NF: (a) CV curves under different scan rates,

(b) linear relation between log (scan rate) and log (peak current), (c) capacitive contribution ratios,

and (d) pseudocapacitive contribution (dark red region) at 2.0 mV s−1.

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Figure S27. VS4 nanoparticles (a) discharge–charge voltage profiles at a current density of 2 A

g−1, (b) CV curves under scan rates at 0.2-1.0 mV s−1, (c) capacitive contribution ratios and (d)

pseudocapacitive contribution (dark red region) at 1.0 mV s−1.

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Figure S28. Characterizations of VS4-HNS in fully discharged state: (a-b) SEM images after 10

cycles, (c-e) HRTEM images and (f) SAED pattern.

Figure S29. FESEM images of the recycled hollow VS4 nanospheres (HNS) after 1000 cycles.

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Figure S30. (110) plane single layer Surface structure model (a, b) and Na+ adsorption site (c).

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Table S1. BET surface area, total pore volume, micropore volume and adsorption average pore

width of VS4-NS, VS4-HNS, VS4-NF.

Morphology BET surface area (m2 g–1) Total pore volume (cm3 g–1) Adsorption average pore width (nm)

VS4-NS 19.384 0.022 3.817

VS4-HNS 23.520 0.062 3.031

VS4-NF 54.637 0.256 3.399

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Table S2. Comparison of different VS4 materials used as anode for Sodium ion batteries.

No Anode Capacities Current Density Cycles Capacities after Rate capacity (mAh g−1)
Ref.
materials (mAh g−1) (mA g−1) number cycling (mAh g−1)

1 VS4/GS —— 500 1200 222 —— S6

2 VS4-G 380 1000 700 232 530, 482.5 408.3, 345.6, 270.1 at S7

0.1, 0.2, 0.6, 1.2, 2.4 A g−1

3 VSG2 —— 500 300 402 605, 547, 507, 469, 460, 446 at S8

0.1, 0.2, 0.4, 0.6, 0.8, 1 A g−1

4 VS4 230 200 120 301 204, 196, 165, 145, 127 at 0.1, S9

0.2, 0.5, 1.0, 2.0 A g−1

5 VS4-5 423 200 230 412 408, 370, 345, 293, 201 at 0.2, S10

0.5, 1.0, 2.0, 5.0 A g−1

6 SB-VS4 —— 1000 1000 268 339, 315, 285, 276, 270 at 0.1, S11

0.2, 0.5, 1.0, 2.0 A g−1

7 PNBS-VS4 438 5000 1000 309 486, 430, 356, 312 at 0.2, 0.5, S12

1.0, 2.0 A g−1

8 VS4-20h —— 1000 400 410 500, 475, 452, 428, 398, 345, 288 S13

at 0.1, 0.2, 0.5,1, 2, 5, 10 A g−1

9 VS4 —— 10000 1000 258 —— S14

10 VS4/MWCNT —— 200 70 680 475, 450, 417, 382, 368 at 0.2, S15

0.5, 1, 2, 5 A g−1

11 VS4-CN-Hs —— 5000 1000 386 847, 735, 674, 597, 479, 444 at S16

0.2, 0.5, 1.0, 2.0, 5.0, 10 A g−1

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12 VS4-NS 1005 200 100 1000 806.6, 792.2, 729.4, 690.7, 545.9 This

at 0.2, 0.5, 1.0, 2.0, 5.0 A g−1 work

13 VS4-HNS 1117 2000 1000 1129 916.8, 852.0, 809.2, 775.7, 748.2 This

at 0.2, 0.5, 1.0, 2.0, 5.0 A g−1 work

14 VS4-NF 1206 200 100 1100 835.3, 646.9, 453.7, 371.6,260.4 This

at 0.2, 0.5, 1.0, 2.0, 5.0 A g−1 work

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Table S3. The detail information of V and S binding energies, intensity ratios of V 2p and S 2p

and surface composition of V and S of anode materials during charge/discharge.

V binding energy V 2P 1/2:3/2 V composition S binding energy S 2P 1/2:3/2 S composition

V1 515.5 1:1.2 0.3 161.2 1:1.3 0.7

V3 516.1 1:1.16 0.4 161 1:1.4 0.6

V5 516.7 1:1.2 0.37 160.6 1:1.24 0.63

V6 516.3 1:1.1 0.35 161.1 1:1.25 0.65

V7 515.8 1:1.1 0.39 161.7 1:1.28 0.61

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