Metal-Organic Framework Derived Iron Sulfide-Carbon Core-Shell Nanorods as a Conversion-Type Battery Material

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Supporting Information Metal-Organic Framework Derived Iron Sulfide-Carbon Core-Shell Nanorods as a Conversion-Type Battery Material Wei Huang,, Shuo Li, Xianyi Cao, Chengyi Hou, Zhen Zhang, Jinkui Feng, Lijie Ci, Pengchao Si,*, Qijin Chi *, SDU & Rice Joint Center for Carbon Nanomaterials, Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials, Ministry of Education, School of Materials Science and Engineering, Shandong University, Jinan 250061, P. R. China. Department of Chemistry, Technical University of Denmark, DK-2800 Kongens Lyngby, Denmark. * Corresponding authors. E-mail address: pcsi@sdu.edu.cn (P.S.) and cq@kemi.dtu.dk (Q.C.) S1

I. Supporting Figures and Table Figure S1. (a) XRD pattern and (b) FT-IR spectrum of the precursor MIL-88-Fe. S2

Figure S2. Comparison of the XRD patterns of the products obtained with various mass ratios of the reactants: (a) MIL-88-Fe heated at 600 o C for 4h in the absence of sulfur powder, (b) the product obtained with the mass ratio of 3:1 (MIL-88-Fe/Sulfur), and (c) the product obtained with the mass ratio of 2:1 (MIL-88-Fe/Sulfur). S3

Figure S3. Typical SEM image of MIL-88-Fe MOF precursor. S4

Figure S4. EDS spectrum of C@Fe 7 S 8 composite. Insets are the elemental ratio of the components and a SEM image of C@Fe 7 S 8 composite. The EDS spectrum was recorded in the boxed part of the SEM image. S5

Figure S5. Line scans of a single C@Fe 7 S 8 composite nanorod. Inset is a TEM image of C@Fe 7 S 8 composite in which the scanned area is marked. S6

Figure S6. (a) SEM image of Fe 3 O 4 /C composite. (b) Cycling performance of the Fe 3 O 4 /C composite at a current rate of 500 ma g -1. the product was obtained via same protocol without sulfur. S7

Figure S7. The XRD patterns of C@Fe 7 S 8 electrode material before and after 50 charge-discharge cycles at 100 ma g -1. S8

Figure S8. SEM images of C@Fe7S8 based anode material: (a) before cycling tests, and (b) after 50 charge-discharge cycles at 100 ma g-1. S9

Figure S9. EDS mapping of the element distribution of C@Fe 7 S 8 based anode electrodes: (a-d) before cycling tests (see Figure S7a) and (e-h) after 50 charge-discharge cycles at 100 ma g -1 (see Figure S7b). S10

Figure S10. (a, b) TEM images of C@Fe 7 S 8 electrode material after 50 charge-discharge cycles at 100 ma g -1. S11

Table S1. Comparison of electrochemical performances of the C@Fe 7 S 8 composite with previously reported iron sulfides related systems. Composite Synthesis method Current Cycle number Capability (mah g -1 ) Ref. C@FeS nanosheets Templated method 100 ma g -1 100 623 3 FeS Nanodots/ carbon nanowires rgo/fes nanoparticles Electrospinning/ hydrothermal Solution-based method /heating 0.5 C 50 400 4 100 ma g -1 40 978 5 FeS microsheet Solution-based method 100 ma g -1 20 677 6 FeS@C/carbon cloth FeS 2 /rgo microspheres Fe 1-x S/porous carbon Solution-based method/heating Solution-based method/heating Solution-based method/heating 0.15C 100 370 7 890 ma g -1 300 970 8 100 mag -1 200 1185 9 Fe 3 S 4 microcrystals Hydrothermal method 100 ma g -1 100 563 10 Fe 0.46 S/C microspheres Fe 7 S 8 @C nanospheres C@Fe 7 S 8 nanorods Hydrothermal method/heating Hydrothermal method/heating Solid-state direct sulfurizing iron based MOF 50 ma g -1 50 736 11 100 ma g -1 50 695 12 500 ma g -1 170 1148 This Work S12

II. Supporting references (1) Xu, X.; Cao, R.; Jeong, S.; Cho, J. Spindle-Like Mesoporous α-fe 2 O 3 Anode Material Prepared from MOF Template for High-Rate Lithium Batteries. Nano Lett. 2012, 12, 4988-4991. (2) Banerjee, A.; Aravindan, V.; Bhatnagar, S.; Mhamane, D.; Madhavi, S.; Ogale, S. Superior Lithium Storage Properties of α-fe 2 O 3 Nano-Assembled Spindles. Nano Energy 2013, 2, 890-896. (3) Xu, C.; Zeng, Y.; Rui, X.; Xiao, N.; Zhu, J.; Zhang, W.; Chen, J.; Liu, W.; Tan, H.; Hng, H. H. Controlled Soft-Template Synthesis of Ultrathin C@FeS Nanosheets with High-Li-Storage Performance. ACS Nano 2012, 6, 4713-4721. (4) Zhu, C.; Wen, Y.; van Aken, P. A.; Maier, J.; Yu, Y. High Lithium Storage Performance of FeS Nanodots in Porous Graphitic Carbon Nanowires. Adv. Funct. Mater. 2015, 25, 2335-2342. (5) Fei, L.; Lin, Q.; Yuan, B.; Chen, G.; Xie, P.; Li, Y.; Xu, Y.; Deng, S.; Smirnov, S.; Luo, H. Reduced Graphene Oxide Wrapped FeS Nanocomposite for Lithium-Ion Battery Anode with Improved Performance. ACS Appl. Mater. Interfaces 2013, 5, 5330-5335. (6) Xing, C.; Zhang, D.; Cao, K.; Zhao, S.; Wang, X.; Qin, H.; Liu, J.; Jiang, Y.; Meng, L. In Situ Growth of FeS Microsheet Networks with Enhanced Electrochemical Performance for Lithium-Ion Batteries. J. Mater. Chem. A 2015, 3, 8742-8749. (7) Wei, X.; Li, W.; Shi, J. A.; Gu, L.; Yu, Y. FeS@C on Carbon Cloth as Flexible Electrode for Both Lithium and Sodium Storage. ACS Appl. Mater. Interfaces 2015, 7, 27804-27809. (8) Xue, H.; Yu, D. Y. W.; Qing, J.; Yang, X.; Xu, J.; Li, Z.; Sun, M.; Kang, W.; Tang, Y.; Lee, C.-S. Pyrite FeS 2 Microspheres Wrapped by Reduced Graphene Oxide as High-Performance Lithium-Ion Battery Anodes. J. Mater. Chem. A 2015, 3, 7945-7949. (9) Wang, C.; Lan, M.; Zhang, Y.; Bian, H.; Yuen, M.-F.; Ostrikov, K.; Jiang, J.; Zhang, W.; Li, Y. Y.; Lu, J. Fe 1 x S/C Nanocomposites from Sugarcane Waste-Derived Microporous Carbon for High-Performance Lithium Ion Batteries. Green Chem. 2016, 18, 3029-3039. (10) Li, G.; Zhang, B.; Yu, F.; Novakova, A. A.; Krivenkov, M. S.; Kiseleva, T. Y.; Chang, L.; Rao, J.; Polyakov, A. O.; Blake, G. R.; de Groot, R. A.; Palstra, T. T. M. High-Purity Fe 3 S 4 Greigite Microcrystals for Magnetic and Electrochemical Performance. Chem. Mater. 2014, 26, 5821-5829. (11) Wu, B.; Song, H.; Zhou, J.; Chen, X. Iron Sulfide-Embedded Carbon Microsphere Anode Material with High-Rate Performance for Lithium-Ion Batteries. Chem. Commun. 2011, 47, 8653-8655. (12) Zhang, K.; Zhang, T.; Liang, J.; Zhu, Y.; Lin, N.; Qian, Y. A Potential Pyrrhotite (Fe 7 S 8 ) Anode Material for Lithium Storage. RSC Adv. 2015, 5, 14828-14831. S13