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

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1 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 , P. R. China. Department of Chemistry, Technical University of Denmark, DK-2800 Kongens Lyngby, Denmark. * Corresponding authors. address: pcsi@sdu.edu.cn (P.S.) and cq@kemi.dtu.dk (Q.C.) S1

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

3 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

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

5 Figure S4. EDS spectrum of 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

6 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

7 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

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

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

10 Figure S9. EDS mapping of the element distribution of 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

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

12 Table S1. Comparison of electrochemical performances of the 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 FeS Nanodots/ carbon nanowires rgo/fes nanoparticles Electrospinning/ hydrothermal Solution-based method /heating 0.5 C ma g FeS microsheet Solution-based method 100 ma g 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 ma g mag Fe 3 S 4 microcrystals Hydrothermal method 100 ma g Fe 0.46 S/C microspheres Fe 7 S nanospheres C@Fe 7 S 8 nanorods Hydrothermal method/heating Hydrothermal method/heating Solid-state direct sulfurizing iron based MOF 50 ma g ma g ma g This Work S12

13 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, (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, (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, (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, (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, (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, (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, (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, (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, (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, (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, (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, S13