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

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1 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, , China

2 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.

3 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.

4 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.

5 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 ev and 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.

6 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 ev in the electrolyte of Sup P/70S cell, and there is nearly no peak at 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.

7 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.

8 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% Ref. S2 GN CNT/S 72% Ref. S3 PEDOT-C/S 63% Ref. S4 Ti 4 O 7 /S 60% Ref. S5 TiC/S 70% Ref. S6 MnO 71% Ref. S7 TiO@C-HS/S 70% Ref. S8 TiN/S 58.8% Ref. S9 C@WS 2 /S 70% Ref. S10 CH@LDH/S 75% Ref. S11 HMT@CNT/S 56% Ref. S12 MCM/Nb 2 O 5 /S 60% Ref. S13 Co 4 N/S 72.3% 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 Ref. S2 GN CNT/S 72% 0.5C Ref. S3 PEDOT-C/S 63% 0.5C Ref. S4 Ti 4 O 7 /S 60% 0.5C Ref. S5 TiC/S 70% 0.5C Ref. S6 MnO 71% 0.5C Ref. S7 TiO@C-HS/S 70% 0.5C Ref. S8 TiN/S 58.8% 0.5C Ref. S9 C@WS 2 /S 70% 2C Ref. S10 CH@LDH/S 75% 1C Ref. S11 HMT@CNT/S 56% 1C Ref. S12 MCM/Nb 2 O 5 /S 60% 0.5C Ref. S13 MnO 2 /S 75% 1C Ref. S14 0.5C Co 4 N/S 72.3% 1C This work 2C C

9 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 Ref. S % 1C hcnc/s 78.9% 2C Ref. S % 0.6C NMP/S 90% 0.1C Ref. S17 1C D NG/S 87.6% 1C Ref. S18 90% 0.5C Co4N/S 1C C This work 95% 1C C 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, (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, (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: (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, (S5) Pang, Q.; Kundu, D.; Cuisinier, M.; Nazar, L. F. Surface-Enhanced Redox Chemistry of

10 Polysulphides on a Metallic and Polar Host for Lithium-Sulphur Batteries. Nat. Commun. 2014, 5, (S6) Liang, X.; Garsuch, A.; Nazar, L. F. Sulfur Cathodes Based on Conductive MXene Nanosheets for High-Performance Lithium-Sulfur Batteries. Angew. Chem. Int. Ed. 2015, 54, (S7) Li, Z.; Zhang, J. T.; Lou, X. W. Hollow Carbon Nanofibers Filled with MnO 2 Nanosheets as Efficient Sulfur Hosts for Lithium-Sulfur Batteries. Angew. Chem. Int. Ed. 2015, 54, (S8) Li, Z.; Zhang, J. T.; Guan, B. Y.; Lou, X. W. A Sulfur Host Based on Titanium Monoxide@ Carbon Hollow Spheres for Advanced Lithium-Sulfur Batteries. Nat. Commun. 2016, 6, (S9) Cui, Z. M.; Zu, C. X.; Zhou, W. D.; Goodenough, J. B. Mesoporous Titanium Nitride-Enabled Highly Stable Lithium-Sulfur Batteries. Adv. Mater. 2016, 28, (S10) Lei, T. Y.; Chen, W.; Huang, J. W.; Xiong, J. Multi Functional Layered WS2 Nanosheets for Enhancing the Performance of Lithium-Sulfur Batteries. Adv. Energy Mater. 2016, 6, (S11) Zhang, J.; Hu, H.; Li, Z.; Lou, X. W. Double-Shelled Nanocages with Cobalt Hydroxide Inner Shell and Layered Double Hydroxides Outer Shell as High-Efficiency Polysulfide Mediator for Lithium-Sulfur Batteries. Angew. Chem. Int. Ed. 2016, 55, (S12) Huang, J. Y.; Kim, H. M.; Manthiram, A.; Sun, Y. K.; High-Energy, High-Rate, Lithium Sulfur Batteries: Synergetic Effect of Hollow TiO 2 -Webbed Carbon Nanotubes and a Dual Functional Carbon-Paper Interlayer. Adv. Energy Mater. 2016, 6, (S13) Tao, Y. Q.; Wei, Y. J.; Liu, Y.; Long, D. H. Kinetically-Enhanced Polysulfide Redox

11 Reactions by Nb 2 O 5 Nanocrystals for High-Rate Lithium-Sulfur Battery. Energy Environ. Sci. 2016, 9, (S14) Liang, X.; Hart, C.; Pang, Q.; Nazar, L. F. A Highly Efficient Polysulfide Mediator for Lithium-Sulfur Batteries. Nat. Commun. 2015, 6, (S15) Zheng, Z. M.; Guo, H. C.; Fang, X. L.; Zheng, N. F. High Sulfur Loading in Hierarchical Porous Carbon Rods Constructed by Vertically Oriented Porous Graphene-Like Nanosheets for Li-S Batteries. Adv. Funct. Mater. 2016, 26, (S16) Lyu, Z.; Xu, D.; Yang, L.; Che, R.; Feng, R.; Zhao, J.; Li, Y.; Wu, Q.; Wang, X.; Hu, Z. Hierarchical Carbon Nanocages Confining High-Loading Sulfur for High-Rate Lithium-Sulfur Batteries. Nano Energy 2015, 12, (S17) Du, W. C.; Yin, Y. X.; Zeng, X. X.; Shi, J. L.; Zhang, S. F.; Wan, L. J.; Guo, Y. G. Wet Chemistry Synthesis of Multidimensional Nanocarbon Sulfur Hybrid Materials with Ultrahigh Sulfur Loading for Lithium-Sulfur Batteries. ACS Appl. Mater. Interfaces 2016, 8, (S18) Wang, C.; Su, K.; Guo, W; Huang, Y. High Sulfur Loading Composite Wrapped by 3D Nitrogen-Doped Graphene as a Cathode Material for Lithium-Sulfur Batteries. J. Mater. Chem. A 2014, 2,