JOUL, Volume 2 Supplemental Information A Two-Dimensional Porous Carbon-Modified Separator for High-Energy-Density Li-S Batteries Fei Pei, Lele Lin, Ang Fu, Shiguang Mo, Daohui Ou, Xiaoliang Fang, and Nanfeng Zheng
Supporting Information Figure S1. SEM images of GO (A) and GO@SiO 2 (B). After SiO 2 coating process, the ultrathin and wrinkled GO templates were converted into the flat nanosheets, and no silica particles or GO templates were observed, indicating that SiO 2 have been coated onto GO. Figure S2. SEM images of the G@PC nanosheets. Figure S3. Typical TEM images of the G@PC nanosheets.
Figure S4. Ultrathin-section TEM image of the G@PC nanosheets. Figure S5. Typical AFM image of the G@PC nanosheets.
Figure S6. Schematic illustration for the synthesis of the G@PC and PC naosheets. Inset: the optical photographs of the GO@SiO 2 and SiO 2 nanosheets. Figure S7. SEM images of the PC nanosheets.
Figure S8. Characterizations of the PC nanosheets. (A) N 2 sorption isotherm, (B) pore-size distribution, (C) XPS spectrum, and (D) N 1s XPS spectrum of G@HMCN. The BET surface area and N content of the PC nanosheets are 2094 m 2 g -1 and 4.5 at%, respectively. Figure S9. UV-Vis absorption spectra of the pure THF sides in the permeation experiments.
Figure S10. The possible pathways for the mass transfer behaviors of the G@PC/PP and PC barrier layers. Figure S11. The thermogravimetric curve of the CB/S composite.
Figure S12. Charge/discharge curves of the CB/S cathodes with different separators at 0.2 C. (A) the PC/PP cell, (B) the G/PP cell, (C) the CNT/PP cell, (D) the PC/PP cell, and (E) the PP cell. Marks: I, the 3 rd cycle; II, the 10 th cycle; the 50 th cycle; and the 100 th cycle. Figure S13. The Nyquist plots of the CB/S cathodes with different separators. (A) before cycling and (B) after ten cycles at 0.2 C. The semicircle in each curve is related to the charge-transfer resistance.
Figure S14. The first CV curves of the CB/S cathodes with different separators. (A) G@PC/PP, (B) PC/PP, (C) G /PP, (D) CNT/PP, (E) CB/PP, and (F) PP. In the cathodic scans, the peaks i and ii are attributed to the typical multistep reduction process from S 8 to the soluble polysulfides Li 2 S 4-8 to the insoluble products Li 2 S 2 /Li 2 S 2. The peaks iii and iv in the anodic scans are derived from the converse oxidation process. The peak values of cathodic currents decreased in the order of G@PC/PP > PC/PP > G/PP > CNT/PP > CB/PP > PP.
Figure S15. Comparisons of the G@PC with 4.5% of N (G@PC-4.5%N) and G@PC with 2.0% of N (G@PC-2.0%N). (A) polysulfide solution treated with the same weights of G@PC-4.5%N and G@PC-2.0%N, (B) polysulfide permeation of the G@PC-4.5%N and G@PC-2.0%N modified separators, (C) cycling performances of the CB/S cathodes with the G@PC-4.5%N, G@PC-2.0%N, and graphene modified separators at 0.2 C. Figure S16. Characterizations of the CB/S cathodes after 100 cycles at 0.2 C. The coin cells were disassembled after full charge, and the separators were directly photographed without any treatment. The top sides of these separators were faced toward Li metal anode.
Figure S17. SEM images of the Li metal anodes after 100 cycles at 0.2 C. The G@PC/PP (A), PC/PP (B), G/PP (C), CNT/PP (D), CB/PP (E), and PP (E) cells were disassembled in an Ar-flled glove box, and the Li-metal anodes were washed gently with DOL/DME solvent. After being dried in the glove box at room temperature, the Li-metal anodes were transferred into a sealed container for further SEM observation.
Figure S18. Electrochemical performance of the G@PC/PP and /PP coin cells after 72 hr storage. (A, B) charge/discharge curves at 1 C, (C) cycling stabilities at 1 C. Figure S19. Charge/discharge curves of the CB/S cathodes with different separators at various rates. (A) the PC/PP cell, (B) the G/PP cell, (C) the CNT/PP cell, (D) the PC/PP cell, and (E) the PP cell.
Figure S20. Charge/discharge curves of the G@PC/PP cell at 1 C. Figure S21. The capacity retention comparison between the CB/S cathode decorated with G@PC/PP and the representative sulfur composite cathodes.
Figure S22. Charge/discharge curves of the CNT/S-6.0 and CNT/S-9.0 cells at 0.2 C. Figure S23. Cycling performances of the CNT/S-14.0 and CNT/S-12.0 coin cells at 0.2 C. Figure S24. The capacity comparison between the CNT/S cathode decorated with G@PC/PP and the representative sulfur composite cathodes.
Figure S25. Charge/discharge curves of the CNT/S-6.0 cell at 0.5 C. Figure S26. Cycling performance of the G@PC/PP coin cell with 9 L mg -1 S of electrolyte.
Table S1. The performance of the Li-S batteries with the barrier modified separators. Barrier Weight of barrier (mg cm -2 ) Thickness of barrier (μm) S loading (mg cm -2 ) S content (wt%) a S content (wt%) b The maximal rate (C) c Capacity (mah g -1 ) Ref Graphene 1.3 30 1.5~2.1 70 44~49 4 512 S1 Super P 0.61 60 0.70~1.0 60 39~44 4 417 S2 Graphene oxide (GO) Nafion solution Mesoporous carbon 0.29 0.75 1~1.2 35 27~32 2 430 S3 0.7 / 0.53 50 30 5 ~500 S24 0.5 27 1.55 49 41 2 800 S25 Li 4Ti 5O 12/ graphene ~0.35 35 1.2 60 51 2 709 S26 Super P 0.38~0.52 10 1.0~1.4 63 ~50 5 620 S27 LDH/ graphene 0.3 2 1.1~1.3 63 54~55 2 709 S28 CNT/SiO 2 /CNT 0.13 3 1.1 50 47 3 ~780 S29 HKUST-5/GO 0.3 10 0.6~0.8 56 44~46 3 488 S30 G@PC d 0.075 0.9 3.5 64 63 5 688 This work (a) the S contents of the sulfur composite cathodes, (b) the S contents of the sulfur composite cathodes after decorated with the barrier modified separator, (c) 1C = 1675 ma g -1, (d) the discharge capacities of G@PC at 1, 2, 3 C and 4C were 882, 842, 767 and 703 mah g -1, respectively.
Table S2. The comparisons of the sulfur composite cathodes (sulfur loading 3.5 mg cm -2 ) Cathodes Sulfur loaded in Co-C-N S loaded in C 3 N 4 nanosheets S loaded in MnO 2 @hollow CNF* S loaded in carbon nanobowls S content (cathodes) S loading (mg cm -2 ) 49% 2 60% 3.0 49.7% 3.5 49% 1.1~1.5 S loaded in TiN 50% 1.0 S loaded in hierarchical porous carbon rods S loaded in Co(OH) 2 @LDH nanocages Sulfur loaded in CNT-NH 2 S loaded in MOFs/CNT** 63% 1.5 52.5% 3.0 56% 1.2 40% 1 CB/S 64% 3.5 Capacity (mah g -1 ) 625 (500 th cycle at 1 C) ~600 (175 th cycle at 0.2 C) 662 (300 th cycle at 0.5 C) 706 (400 th cycle at 1 C) 644 (500 th cycle at 0.5 C) 700 (300 th cycle at 0.2 C) 491 (100 th cycle at 0.5 C) ~680 (100 th cycle at 1 C) ~758 (500 th cycle at 0.2 C). 754 (500 th cycle at 1 C) Ref S4 S14 S31 S32 S33 S34 S35 S36 S37 This work *carbon nanofibers (CNF); * Metal organic frameworks (MOFs).
Table S3. The comparisons of the sulfur composite cathodes (sulfur loading > 3.5 mg cm -2 ) Cathodes S content S loading (cathodes) (mg cm -2 ) Li 2 S 6 loaded in 3D N/S-doped 63~72.5% 4.6 graphene S loaded in CNF paper 72.3% 10.8 S loaded in CNT paper 52.9% 11.4 S loaded in hollow Carbon spheres and 62% 3.9 graphene S loaded in porous CNF 72% 4.5 S loaded in hollow carbon 67.5% 10.8 fiber foam 6 CNT/S 70% 12 Capacity (mah g -1 ) 550 (500 th cycle at 0.5 C) ~760 (50 th cycle at 0.066 C) 650 (100 th cycle at 0.2 C) 520 (200 th cycle at 0.2 C) 680 (200 th cycle at 0.2 C) 852 (200 th cycle at 0.2 C) 793 (400 th cycle at 0.5 C) 1007 (100 th cycle at 0.2 C) Ref S15 S16 S17 S18 S19 S38 This work
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