Supporting Information. Co 4 N Nanosheets Assembled Mesoporous Sphere as a Matrix for Ultrahigh Sulfur Content Lithium Sulfur Batteries

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Supporting Information Co 4 N Nanosheets Assembled Mesoporous Sphere as a Matrix for Ultrahigh Sulfur Content Lithium Sulfur Batteries Ding-Rong Deng, Fei Xue, Yue-Ju Jia, Jian-Chuan Ye, Cheng-Dong Bai, Ming-Sen Zheng* and Quan-Feng Dong* State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, ichem (Collaborative Innovation Center of Chemistry for Energy Materials) Xiamen, Fujian, 361005, China

Figure S1. XRD patterns of Co 3 O 4 phase (a) and Co 4 N phase (b) Figure S2. The EDS by SEM of Co 4 N phase. It shows that the atomic ratio of Co and N is about 4:1.

Figure S3. The TEM images of Co 3 O 4 phase(a)(b) and Co 4 N phase (c)(d). Figure S4. TG curve of Co 4 N/70S (a), Co 3 O 4 /70S (b), Co/70S (c) and sup P/70S (d). The lost weights have given the sulfur loadings of 72.32%, 73.62%, 72.67% and 73.33%, respectively.

Figure S5. The characterization of the Co 4 N/70S sample. (a) XRD patterns of Co 4 N/70S, (b) (c) SEM images of Co 4 N/70S (d-g) SEM image and corresponding elemental mappings of Co 4 N/70S. Figure S6. The charge and discharge capacity and Coulombic efficiency versus cycle number at current densities of 1 C.

Figure S7. Rate capability of Co 4 N/70S, Co 3 O 4 /70S, Co/70S and sup P/70S at different current rates. Figure S8. S 2p X-ray photoelectron spectroscopy (XPS) of the metal lithium in Sup P/70S (a) and Co4N/70S (b) cell after 100 cycles. The peaks in the range of 167 171 ev and 159 164 ev in are assigned to electrolyte and Li2Sx species, respectively. It is clear that the signals of polysulfide, wether for Sup P/70S or Co4N/70S, are existing. However, the Li2Sx intensity on lithium anode in Co4N/70S cell is much lower than that in Sup P/70S cell.

Figure S9. S 2p X-ray photoelectron spectroscopy (XPS) of the electrolyte in Sup P/70S (a) and Co4N/70S (b) cell after 100 cycles. There are obvious peak around 160-164 ev in the electrolyte of Sup P/70S cell, and there is nearly no peak at 160-164 ev in the electrolyte of Co4N/70S cell. It shows that the Co 4 N can efficient reduce the shuttle effect during the discharge and charge process.

Figure S10. TG curve of Co 4 N/90S (a), Co 3 O 4 /90S (b) and Co 4 N/95S (c). The lost weights have given the sulfur loadings of 89.64%, 89.02% and 94.88%, respectively.

Table S1 Rate capabilities of the Li-S cathodes. S cathode S 0.1 C 0.2 C 0.5 C 1 C 2 C References content Capacity (mah g -1 ) Capacity (mah g -1 ) Capacity (mah g -1 ) Capacity (mah g -1 ) Capacity (mah g -1 ) CMK 3 /S 70% 1300 Ref. S1 N-HPCB/S 70% 1065 882 785 673 Ref. S2 GN CNT/S 72% 1492 1172 993 854 583 Ref. S3 PEDOT-C/S 63% 1200 1100 1020 972 842 Ref. S4 Ti 4 O 7 /S 60% 1200 1070 1000 830 Ref. S5 TiC/S 70% 1450 1210 1100 1010 Ref. S6 MnO 2 @HCF/S 71% 1161 1010 890 690 Ref. S7 TiO@C-HS/S 70% 1146 1029 910 800 655 Ref. S8 TiN/S 58.8% 1121 899 776 Ref. S9 C@WS 2 /S 70% 1581 1318 1165 931 596 Ref. S10 CH@LDH/S 75% 1068 800 650 500 Ref. S11 HMT@CNT/S 56% 1550 1300 1070 1010 888 Ref. S12 MCM/Nb 2 O 5 /S 60% 1358 1242 1145 979 Ref. S13 Co 4 N/S 72.3% 1659 1299 1140 1010 882 This work Table S2 Cyclabilities of the S cathodes at about 70% S content. S cathode S Rate cycles Capacity References content (mah/g) N-HPCB/S 70% 1C 300 706 Ref. S2 GN CNT/S 72% 0.5C 500 660 Ref. S3 PEDOT-C/S 63% 0.5C 300 707 Ref. S4 Ti 4 O 7 /S 60% 0.5C 100 850 Ref. S5 TiC/S 70% 0.5C 100 965 Ref. S6 MnO 2 @HCF/S 71% 0.5C 300 662 Ref. S7 TiO@C-HS/S 70% 0.5C 500 630 Ref. S8 TiN/S 58.8% 0.5C 500 644 Ref. S9 C@WS 2 /S 70% 2C 500 582 Ref. S10 CH@LDH/S 75% 1C 100 653 Ref. S11 HMT@CNT/S 56% 1C 100 1000 Ref. S12 MCM/Nb 2 O 5 /S 60% 0.5C 200 913 Ref. S13 MnO 2 /S 75% 1C 200 800 Ref. S14 0.5C 100 1100 Co 4 N/S 72.3% 1C 100 1000 This work 2C 1000 761 5C 300 587

Table S3 Cyclabilities of the S cathodes at above 75% S content. S content S Rate cycles Capacity References content (mah/g) HPCR/S 80% 1C 300 700 Ref. S15 88.8% 1C 100 630 hcnc/s 78.9% 2C 300 580 Ref. S16 89.9% 0.6C 100 411 NMP/S 90% 0.1C 50 667 Ref. S17 1C 50 612 3D NG/S 87.6% 1C 200 670 Ref. S18 90% 0.5C 100 920 Co4N/S 1C 100 810 2C 800 690 This work 95% 1C 100 640 2C 800 540 REFERENCES (S1) Ji, X. L.; Lee, K. T.; Nazar, L. F. A highly Ordered Nanostructured Carbon-Sulphur Cathode for Lithium-Sulphur Batteries. Nat. Mater. 2009, 8, 500 506. (S2) Pei, F.; An, T. H.; Tang, X. L.; Zheng, N. F. From Hollow Carbon Spheres to N-Doped Hollow Porous Carbon Bowls: Rational Design of Hollow Carbon Host for Li-S Batteries. Adv. Energy Mater. 2016, 6, 1502039 (S3) Zhang, Z.; Kong, L.-L.; Liu, S.; Li, G. R., Gao, X.-P. A High-Efficiency Sulfur/Carbon Composite Based on 3D Graphene Nanosheet@Carbon Nanotube Matrix as Cathode for Lithium-Sulfur Battery. Adv. Energy Mater. 2017, 7, DOI:20160254 (S4) Li, W. Y.; Liang, Z.; Lu, Z. D.; Yao, H. B., Seh, Z. W., Yan, K., Zheng, G. Y.; Cui, Y. A Sulfur Cathode with Pomegranate-Like Cluster Structure. Adv. Energy Mater. 2015, 5, 1500211. (S5) Pang, Q.; Kundu, D.; Cuisinier, M.; Nazar, L. F. Surface-Enhanced Redox Chemistry of

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