Copyright WILEY VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2016. Supporting Information for Adv. Energy Mater., DOI: 10.1002/aenm.201502539 From Hollow Carbon Spheres to N-Doped Hollow Porous Carbon Bowls: Rational Design of Hollow Carbon Host for Li-S Batteries Fei Pei, Taihua An, Jun Zang, Xiaojing Zhao, Xiaoliang Fang,* Minseng Zheng, Quanfeng Dong, and Nanfeng Zheng*
Supporting Information From Hollow Carbon Spheres to N-doped Hollow Porous Carbon Bowls: Rational Design of Hollow Carbon Host for Li-S Batteries Fei Pei, Taihua An, Jun Zang, Xiaojing Zhao, Xiaoliang Fang,* Minseng Zheng, Quanfeng Dong and Nanfeng Zheng* Experimental Section Adsorption of Lithium Polysulfide: Lithium sulfide (Li 2 S) were purchased from Alfa Aesar and Lithium polysulfide (Li 2 S 6 ) was synthesized according to the literature (ACS Nano, 2015, 9, 8504.). Typically, S and Li 2 S with a molar ratio of 5:1 were added into tetrahydrofuran with continuous stirring at room temperature under a nitrogen atmosphere, yielding a deep red solution. In a typical experiment for the adsorption of Li 2 S, 100 mg of the hollow carbon hosts were added to 5 ml of the Li 2 S 6 solution (20 mm). After stirring for 15min, the solid were separated by centrifugation. Figure S1. SEM image of SiO 2 @PB spheres. S1
Figure S2. The distribution of zeta potentials of SiO 2 and SiO 2 @PB spheres. Figure S3. SEM image of SiO 2 @PB/SiO 2 spheres. S2
Figure S4. SEM images: (a) polystyrene@pb spheres, (b) commercial Fe 2 O 3 coated with PB layer, (c) commercial NiO coated with PB layer. Figure S5. Schematic illustration for the selective synthesis of HCS, N-HCS, N-HPCS, and N-HPCB. S3
Figure S6. The size distribution of N-HPCB particles dispersed in water. Figure S7. (a) The change of BET surface areas versus the dosage of TEOS: when TOES < 0.6 ml, the ratio of SiO 2 /resorcinol/formaldehyde/eda was 1 g/0.64 g/0.96 ml/0.64 ml; when TOES 0.6 ml, the ratio of SiO 2 /resorcinol/formaldehyde/eda was 1 g/0.4 g/0.6 ml/0.64 ml, (b) the SEM image of the partly concave N-HPCS obtained using 0.5 ml of TOES, (c, d) the SEM images of the shriveled vesicle-like structures obtained using 0.8 and 1.0 ml of TOES, respectively (the arrows point to the damaged portions of vesicle-like structures). S4
Figure S8. XPS spectra: C 1s spectra of (a) N-HCS, (b) N-HPCS, (c) N-HPCB, and O 1s spectra of (d) N-HCS, (e) N-HPCS, (f) N-HPCB. The C 1s and O 1s spectra were assigned according to the reference (Nat. Commun. 2015, 6, 7770. and Adv. Energy Mater. 2015, 5, 1401761.), and the C/O ratios of N-HCS, N-HPCS, and N-HPCB are 16.1, 16.9, and 18.5. Figure S9. SEM images: (a) S/HCS, (b) S/N-HCS and (c) S/N-HPCS. S5
Figure S10. TGA curves: (a) S/HCS, (b) S/N-HCS and (c) S/N-HPCS. Figure S11. Discharge/charge curves at 0.2C: (a) S/HCS, (b) S/N-HCS and (c) S/N-HPCS. S6
Figure S12. Photo: 100 mg of N-HPCS and N-HPCS samples tapped in quartz tubes. To evaluate the tap densities of the four S/HCS composites, a certain quantity of S/HCS powder was placed into a dry measuring cylinder, and the cylinder was then taped at least 200 times (J. Mater. Chem. A, 2015, 3, 16142. and RSC Adv., 2015, 5, 11091.). Based on the mass and the measured volume of the tapped powder, the tap densities of S/HCS, S/N-HCS, and S/N- HPCS were ~ 1.2 g cm -3. In comparison, the tap density of S/HPCB was ~1.6 g cm -3. In addition, during the discharge/charge at 1C, the volume changes of the S/HCS, S/N-HCS, S/N-HPCS, and S/N-HPCB cathodes were ~3.0%, 2.8%, 2.6%, and 2.5%, respectively, indicating that the volumetric change from sulfur to lithium sulfide did not have apparent effect on the as-synthsized S/N-HPCB cathodes. S7
Table S1 Rate capabilities of the S/HCS cathodes S cathode S content charge/discharge rate (C)* capacity (mah/g) References S/N-HPCB 70% 0.2~4 1065~535 This work S/DHCS** 64% 0.1~1 935~350 Ref. S1 S/HCS 70% 0.1~3 1170~450 Ref. S2 Graphene coated S/DHCS 62% 0.2~3 1170~430 Ref. S3 S/N-HCS 67% 0.2~2 1167~655 Ref. S4 S/N-HCS 85% 0.2~2 1040~250 Ref. S5 * 1C=1675 ma/g, ** DHCS=double layered HCS Table S2 Cyclabilities of the S cathodes made form HCS and N-doped carbon S Capacity Capacity S cathode Rate cycles content (mah/g) decay Ref. S/N-HPCB 70% 1C 400 706 0.053% (per cycle) This work S/HCS 70% 1C 100 785 0.1% Ref. S6 PEDOT coated S/HCS* 70% 0.5C 300 707 0.1% Ref. S7 Graphene coated S/DHCS S/hollow-in-hollow structured HCS 62% 0.5C 200 520 0.19% Ref. S3 70% 0.6C 350 780 0.09% Ref. S8 S/N-graphene 65.2% 1C 700 503 0.068% Ref. S9 S/N-CNT** ~50% 1C 450 530 0.08% Ref. S10 S/N-CNT-graphene 52.6% 1C 80 865 0.3% Ref. S11 S/N-doped carbon nanosheets 74% 1C 100 866 0.25% Ref. S12 S/amino-functionalized graphene 60% 0.5C 350 650 0.06% Ref. S13 S/oxygenated carbon nitride 56% 0.5C 500 447 0.1% Ref. S14 S/N-S-doped carbon 70% 0.5C 2C 500 1100 775 365 *PEDOT= poly(3,4-ethylenedioxythiophene) **CNT= carbon nanotubes 0.065% 0.052% Ref. S15 S8
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