In-Situ Fabrication of CoS and NiS Nanomaterials Anchored on. Reduced Graphene Oxide for Reversible Lithium Storage

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Supporting Information In-Situ Fabrication of CoS and NiS Nanomaterials Anchored on Reduced Graphene Oxide for Reversible Lithium Storage Yingbin Tan, [a] Ming Liang, [b, c] Peili Lou, [a] Zhonghui Cui, [a] Xiangxin Guo, [a]* Weiwei Sun [b] and Xuebin Yu [c] [a] State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China; Phone and Fax: +86-21-5566 4581. E-mail: XXGuo@mail.sic.ac.cn [b] Department of Chemical Engineering, School of Environmental and Chemical Engineering, Shanghai University, Shangda Road 99, Shanghai, P. R. China; [c] Department of Materials Science Fudan University Shanghai 200433, China Phone and Fax: +86-21-5566 4581. E-mail: yuxuebin@fudan.edu.cn S1

Figure S1 XRD patterns for In 2 S 3 by heat treatment In(OH) 3 in sulfur atmosphere. S2

Figure S2 XRD patterns for MnS by heat treatment Mn(OH) 2 in sulfur atmosphere. S3

Figure S3 XRD patterns for Cu 1.81 S and CuS 2 by heat treatment Cu(OH) 2 in sulfur atmosphere. S4

Figure S4 XRD patterns for Fe 9 S 10 by heat treatment Fe(OH) 2 in sulfur atmosphere. S5

Figure S5 XRD patterns for ZnS by heat treatment Zn(OH) 2 in sulfur atmosphere. S6

Figure S6 SEM images of as-synthesized a) Co(OH) 2 -rgo and b) Ni(OH) 2 -rgo. S7

Figure S7 SEM image of CoS NFs-rGO a, b) and NiS NPs-rGO c, d). S8

Figure S8 TEM image of NiS NPs-rGO a) and CoS NFs-rGO b). S9

Figure S9 XRD patterns for FeS by heat treatment FeOOH-rGO in sulfur atmosphere. S10

Figure S10 Discharge and charge curves of a) FeS-rGO at the current density of 100 ma g -1 ; rate capabilities of b) FeS-rGO at various current densities between 100 ma g -1 and 2000 ma g -1. S11

Table S1 Compasion of electrochemical performances of the MS-rGO electrodes with previously reported transition metal sulfides-based electrodes. Electrode materials Synthetic method Electrode formulation a Bi 2 S 3 @CNT Carbon-coated FeS nanosheets SnS 2 nanoplates/graphene SnS 2 @graphene nanocables Honeycomb-like MoS 2 /graphene Carbon nanotube/layered MoS 2 nanohybrid network Calcination Surfactant-assisted solution-based method 80:10:10 80:10:10 Cycling stability (A/B/n) b 450/1/100 615/0.1/100 Ref. CVD 80:10:10 650/0.05/30 S3 Electrospinning 100:0:0 720/0.2/350 S4 Hydrothermal 80:10:10 1235/0.2/60 S5 Hydrothermal 80:10:10 1679/1/425 S6 MoS 2 -CMK-3 Hydrothermal 70:20:10 934/0.4/150 S7 MoS 2 nanoplates/carbon nanofibers MoS 2 /mesoporous carbon Sandwich-like MoS 2 @N-doped carbon nanosheets Electrospinning 70:20:10 1007/1/100 S8 Self-polymerization 80:10:10 1113/0.4/500 S9 Self-polymerization 80:10:10 1147/0.1/50 S10 WS 2 nanosheet/cnts Vacuum filtration 80:10:10 862/0.1/50 S11 Ni 3 S 4 nanoparticles/graphene NiS nanoparticles/porous carbon matrices nitrogen-doped-carbon coated CoS 2 3D CoS@PCP/CNTs-600 CoS 2 Nanoparticles/N-Doped Porous Carbon Shell NiS-Graphene CoS-graphene Hydrothermal 80:10:10 1323/0.14/100 S12 Calcination+ Hydrothermal S1 S2 75:10:15 300/0.06/100 S13 solution method 70:20:10 657/0.2/100 S14 MOFs-templated sulfidation 80:10:10 1668/0.2/100 S15 postvulcanizing step 70:20:10 560/0.1/50 S16 Hydrothermal+sulfida tion Hydrothermal+sulfida tion 80:10:10 521/0.1/100 This work 80:10:10 939/0.1/100 This work a Weight ratio of the active material, carbon and binder. PVDF was used as binder if not S12

mentioned. Other values used were specified. b A/B/n means the capacity of A (mah g -1 ) remained after n cycles at the certain currentdensity of B (A g -1 ). References [S1] Ni, J. F.; Zhao, Y.; Liu, T. T.; Zheng, H. H.; Gao, L. J.; Yan, C. L.; Li, L. Strongly Coupled Bi 2 S 3 @CNT Hybrid For Robust Lithium Storage..Adv. Energy Mater., 2014, 4, 1400798. [S2] Xu, C.; Zeng, Y.; Rui, X. H.; Xiao, N.; Zhu, J. X.; Zhang, W. Y.; Chen, J.; Liu, W. L.; Tan, H. T.; Hng, H. H.; Yan, Q. Y. Controlled Soft-Template Synthesis of Ultrathin C@FeS Nanosheets with High-Li-Storage Performance. ACS Nano, 2012, 6, 4713-4721. [S3] Luo, B.; Fang, Y.; Wang, B.; Zhou, J. S.; Song, H. H.; Zhi, L. J. Two Dimensional Graphene SnS 2 Hybrids with Superior Rate Capability for Lithium Ion Storage. Energy Environ. Sci., 2012, 5, 5226-5230. [S4] Kong, D. B.; He, H. Y.; Song, Q.; Wang, B.; Yang, Q.; Zhi, L. J. A Novel SnS 2 @Graphene Nanocable Network for High-Performance Lithium Storage. RSC Adv., 2014, 4, 23372-23376. [S5] Wang, J.; Liu, J. L.; Chao, D. L.; Yan, J. X.; Lin, J. Y.; Shen, Z. X. Self-Assembly of Honeycomb-like MoS2 Nanoarchitectures Anchored into Graphene Foam for Enhanced Lithium-Ion Storage. Adv. Mater., 2014, 26, 7162-7169. [S6] Li, J. Y.; Hou, Y.; Gao, X. F.; Guan, D. S.; Xie, Y. Y.; Chen, J. H.; Yuan, C. A Three-Dimensionally Interconnected Carbon Nanotube/Layered MoS 2 Nanohybrid Network for Lithium Ion Battery Anode with Superior Rate Capacity and Long-Cycle-Life. Nano Energy, 2015, 16, 10-18. [S7] Xu, X.; Fan, Z. Y.; Yu, X. Y.; Ding, S. J.; Yu, D.; (David) Lou, X. W. A Nanosheets-on-Channel Architecture Constructed from MoS 2 and CMK-3 for High-Capacity and Long-Cycle-Life Lithium Storage. Adv. Energy Mater., 2014, 4, 1400902. [S8] Zhu, C. B.; Mu, X. K.; van Aken, P. A.; Yu, Y.; Maier, J. Single-Layered Ultrasmall nanoplates of MoS 2 Embedded in Carbon Nanofibers with Excellent Electrochemical Performance for Lithium and Sodium Storage. Angew. Chem. Int. Ed., 2014, 53, 2152-2155. [S9] Jiang, H.; Ren, D. Y.; Wang, H. F.; Hu, Y. J.; Guo, S. J.; Yuan, H. Y.; Hu, P. J.; Zhang, L.; Li, C. Z. 2D Monolayer MoS 2 Carbon Interoverlapped Superstructure: Engineering Ideal Atomic S13

Interface for Lithium Ion Storage. Adv. Mater., 2015, 27, 3687-3695. [S10] Jeong, J.; Lee, K. G.; Chang, S.; Kim, J. W.; Han, Y. K.; Lee, S. J.; Cho, B. G. Ultrathin Sandwich-Like MoS 2 @N-doped Carbon Nanosheets for Anodes of Lithium Ion Batteries. Nanoscale, 2015, 7, 324-329. [S11] Liu, Y.; Wang, W.; Huang, H. B.; Gu, L.; Wang, Y. W.; Peng, X. S. The Highly Enhanced Performance of Lamellar WS 2 Nanosheet Electrodes upon Intercalation of Single-Walled Carbon Nanotubes for Supercapacitors and Lithium Ions Batteries. Chem. Commun., 2014, 50, 4485-4488. [S12] Mahmood, N.; Zhang, C. Z.; Hou, Y. L. Nickel Sulfide/Nitrogen-Doped Graphene Composites: Phase-Controlled Synthesis and High Performance Anode Materials for Lithium Ion Batteries. Small 2013, 8, 1321-1328. [S13] Wang, Z. Q.; Li, X.; Yang, Y.; Cui, Y. J.; Pan, H. G.; Wang, Z. Y.; Chen, B. L.; Qian, G. D. Highly Dispersed β-nis Nanoparticles in Porous Carbon Matrices by a Template Metal Organic Framework Method for Lithium-Ion Cathode. J. Mater. Chem. A, 2014, 2, 7912-7916. [S14] Peng, S. J.; Li, L. L.; Mhaisalkar, S. G.; Ramakrishna, M.; Srinivasan, S.; Yan. Q. Y. Hollow Nanospheres Constructed by CoS 2 Nanosheets with a Nitrogen-Doped-Carbon Coating for Energy-Storage and Photocatalysis. ChemSusChem 2014, 7, 2212-2220. [S15] Wu, R. B.; Wang, D. P.; Rui, X. H.; Liu, B.; Zhou, K.; Law, A. W. K.; Yan, Q. Y.; Chen, W. Z. In-Situ Formation of Hollow Hybrids Composed of Cobalt Sulfides Embedded within Porous Carbon Polyhedra/Carbon Nanotubes for High-Performance Lithium-Ion Batteries. Adv. Mater., 2015, 27, 3038 3044. [S16] Wang, Q. F.; Zou, R. Q.; Xia, W.; Ma, J.; Qiu, B.; Mahmood, A.; Zhao, R.; Yang, Y. Y. C.; Xia, D. G.; Xu, Q. Facile Synthesis of Ultrasmall CoS 2 Nanoparticles within Thin N-Doped Porous Carbon Shell for High Performance Lithium-Ion Batteries. small, 2015, 11, 2511-2517. S14