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Metal oxide Nanoprism-Arrays assembled in N-Doped Carbon Foamy Nanoplates

to Efficient-Polysulfide-Retention for Ultralong-Cycle-Life Lithium-Sulfur

Batteries

Lu Yao,a Xinwei Dong,b Chaoran Zhang,a Nantao Hu,*a Yafei Zhang*a

a Key Laboratory for Thin Film and Microfabrication Technology of the Ministry of Education,

School of Electronics, Information and Electrical Engineering, Shanghai Jiao Tong University, Dong

Chuan Road No. 800, Shanghai 200240, PR China

b School of Physics and Electronic Engineering, Xinyang Normal University, Nanhu Road No. 237,

Henan 464000, PR China

Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2018

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Supporting Information

Fig. S1. Photographs of NCFN-ZnO-MWCNTs before a) and after b) heat treatments at 200 °C.

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Fig. S2. SEM images of a,b) NCFN-ZnO-MWCNTs, c) AFM measurement and d) thickness profile

of NCFN-MWCNTs on mica.

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Fig. S3. TEM image of NCFN-MWCNTs.

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Fig. S4. a) XRD pattern and b) Raman spectrum of NCFN-MWCNT.

Fig. S5. a) Nitrogen adsorption-desorption isotherms and b) pore-size distribution of NCFN-

MWCNTs.

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Fig. S6. Visual confirmation of polysulfide entrapment at specific discharge depths. a) S@carbon

black, b) NCFN-MWCNTs/80S and c) NCFN-ZnO-MWCNTs/70S.

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Fig. S7. a) Nitrogen adsorption-desorption isotherms and b) pore-size distribution of NCFN-

MWCNTs/80S.

Fig. S8. Top-view SEM images and EDS mapping of NCFN-MWCNTs/80S

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Fig. S9. Cross-section SEM images and EDS mapping of NCFN-ZnO-MWCNTs/70S

Fig. S10. TGA curves of NCFN-MWCNTs and S in N2 atmosphere.

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Fig. S11. Characterization of NCFN-MWCNTs/90S: a) Photograph of NCFN-MWCNTs mixed with

S; b) TGA curve under N2 atmosphere; c) SEM image of NCFN-MWCNTs/90S.

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Fig. S12. Electrochemical performances of NCFN-MWCNTs/90S as cathode for Li−S battery: a) CV

curves at a scan rate of 0.05 mV s-1 and b) rate performance of discharge−charge capacity from 0.5

C to 5 C.

Fig. S13. Characterization and electrochemical properties of NCFN-ZnO-MWCNTs/70S: a) TGA

curve under N2 atmosphere and b) galvanostatic discharge−charge profiles at 0.2 C.

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Figure S14. Rate performance from 0.5 C to 5 C a) and cycling performances as well as coulombic

efficiency at 1 C b) of NCFN-MWCNTs/70S-ZnO.

Figure S15. SEM images of the lithium-metal surface of pristine lithium anode a) and lithium anode

based on NCFN-ZnO-MWCNTs/70S after 500 cycles at 2C b).

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Fig. S16. Photograph of LED bulbs in series lit by Li-S batteries.

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Table S1: The weight percent of Zn in NCFN-ZnO-MWCNTs annealed in a mixture of argon and

ammonia gases (V/V = 3:1) or argon atmosphere by Inductively Coupled Plasma-Atomic Emission

Spectrometry (ICP-AES) measurement

Atmosphere Annealing time (min) The weight percent of Zn

Ar/NH3 0 3.20%

Ar/NH3 10 2.09%

Ar/NH3 20 1.15%

Ar/NH3 30 0.09%

Ar 60 5.66%

Annealing temperature: 800°C

Experimental:All provided samples were dissolved in 5 mL concentrated nitric acid, 1 mL hydrochloric acid

and 1 mL hydrofluoric acid in a 50 mL sealed polytetrafluoroethylene digestion tank. The digestion

reaction was conducted at 200°C for 5 hours. After digestion, the system was cooled down to room

temperature. The solution from the digestion tank was transferred to a 25mL plastic volumetric flask.

Standard stock solutions of 0, 0.5, 1.0, 2.0, 5.0, 10.0mg/L concentration point were used for the

preparation of aqueous standard solutions. The final content of the elements measured in each sample

was determined by the calibration curves.

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Table S2: The comparisons of the carbon-sulfur composites with high sulfur loading. (NA: not

available)

Sample S content(wt. %) Decay rate of per cycle

Capacity after long cycles(mAh g-1)

holey carbon nano-tubesholey carbon nano-

47.4 0.11% (0.5C, 200 cycles) 879

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tubesholey carbon nano-tubesholey carbon nano-tubes

Holy carbon

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nanotubes/ZrO21

Hierarchical porous carbon nanofber2 71 0.067%

(1.5C, 500 cycles) 509

Two-dimensional carbon yolk-shell nanosheet3 73 0.04%

(1C, 500 cycles) 719

Porous carbon nanotube with lightweight

graphene/dithiothreitol476 0.036%

(5C, 1100 cycles) 301

Nanosulfur/graphene/PEDOT:PSS5 56.4 0.04%

(1C, 500 cycles) 806

Carbon nanotube/nanofbrillated

cellulose framework68.1 mg cm-2 0.067%

(0.5C, 1000 cycles) 303.2

N-doped hollow carbon nanospheres7 85 0.12%

(0.2C, 100 cycles) 980

78.90 0.046%(1C, 30th to 300th cycles) 700

Hierarchical porous carbon rods8

88.8 0.1%(1C, 200 cycles) 632

N-doped hollow carbon spheres9 78 0.19%

(0.5C, 200 cycles) 520

NCFN-ZnO-MWCNTs 70 0.032%(2C, 500 cycles) 738.4

80 0.035%(0.5C, 2000 cycles) 324.5

NCFN-MWCNTs(Our work)

90 0.051%(0.5C, 1500 cycles) 264.4

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Table S3. Specific capacities of NCFN-ZnO-MWCNTs/70S, NCFN-MWCNTs/80S and NCFN-

MWCNTs/90S at various rates calculated based on the mass of sulfur and the mass of the composites,

respectively.

Specific capacity (mAh g-1) at various ratesSmaple -

0.5 C 1 C 2 C 3 C 5 C 0.5 C

a 1249.4 1026.7 887.5 777.1 698.6 1085.3NCFN-ZnO-MWCNTs/70S b 874.6 718.7 621.3 544.0 489.0 759.7

a 1062.2 851.4 766.5 707.8 632.6 868.4NCFN-MWCNTs/80S

b 849.8 681.1 613.2 566.2 506.1 694.7a 807.8 723.1 659.3 562.8 355.5 753.6

NCFN-MWCNTs/90Sb 727.0 650.8 593.4 506.5 320.0 678.2

（1C= 1675 mA g-1 ) a: based on the mass of sulfur; b: based on the mass of the composites.

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