Supporting Information

Transcription

1 Supporting Information Cobalt Disulfide Nanoparticles Embedded in Porous Carbonaceous Micro- Polyhedrons Interlinked by Carbon Nanotubes for Superior Lithium and Sodium Storage Yuan Ma,, Yanjiao Ma,, Dominic Bresser,, Yuanchun Ji, Dorin Geiger, Ute Kaiser, Carsten Streb,, Alberto Varzi,*,, Stefano Passerini*,, Helmholtz Institute Ulm (HIU), Helmholtzstrasse 11, D Ulm, Germany Karlsruhe Institute of Technology (KIT), P.O. Box 3640, D Karlsruhe, Germany Institute of Inorganic Chemistry I, Ulm University, Albert-Einstein-Allee 11, D Ulm, Germany Central Facility for Electron Microscopy, Group of Electron Microscopy of Materials Science, Ulm University, Albert-Einstein-Allee 11, D Ulm, Germany * of corresponding author: stefano.passerini@kit.edu (S. Passerini); alberto.varzi@kit.edu (A. Varzi) S1

2 Figure S1. XRD pattern of the Co-C/CNT nanocomposite. S2

3 Figure S2. TEM images of (a) Co-C/CNT and (c) CoS 2 -C/CNT and the corresponding particle size distribution of (b) metallic Co and (d) CoS 2. S3

4 Figure S3. XPS analysis of CoS 2 -C/CNT, including fitting: (a) S 2p 1-3, and (b) Co 2p 1,4. As discussed in the main text, the XPS analysis reveals that some elemental sulfur remains in the sample and does not react with the cobalt comprised in the Co-C/CNT precursor. Additionally, it is observed that some cobalt remains metallic despite the sulfur excess added during the preparation process. The detected sulfate presumably originates from the sample handling and preparation for the XPS analysis, which was conducted under air, since cobalt sulfide rapidly forms cobalt sulfate in contact with oxygen and water. S4

5 Figure S4. EDX mapping images of CoS 2 -C/CNT. S5

6 Figure S5. TGA curve recorded for CoS 2 -C/CNT under air flow (heating rate: 2 C min -1 ). S6

7 Table S1. Co, C and S content determined by ICP-OES and EDX for CoS 2 -C/CNT. ICP [wt%] EDX [wt%] Co C S S7

8 Figure S6. Raman spectrum of the CoS 2 -C/CNT nanocomposite. S8

9 Table S2. Electronic conductivity of various metal oxides/sulfides and composites additionally including carbonaceous materials, as reported in literature. Materials Compound Electronic conductivity (S cm -1 ) Ref. Fe 2 O Metal oxides or carbonaceous metal oxides Fe 2 O 3 -graphene NiO-GNS GNS-CuO Metal sulfides or carbonaceous metal sulfides SnS SnS 2 -RGO NiS-GNS MoS 2 /C CoS/graphene CoS 2 /RGO-CNT CoS 2 -C/CNT 1.2 This work S9

10 Figure S7. (a) Nitrogen-adsorption isotherm at 77 K recorded for CoS 2 -C/CNT. (b) Pore size distribution for CoS 2 -C/CNT, determined from the adsorption isotherm by using the BJH (Barrett-Joyner-Halenda) method. S10

11 Figure S8. Galvanostatic cycling of electrodes based on the Co-C/CNT intermediate (applied specific current: 100 ma g -1 ) to determine the capacity contribution of the comprised carbon, assuming that the subsequent sulfidation process does not have a substantial impact on the carbonaceous species. These electrodes provide a reversible capacity of about 500 mah g -1 in the first cycle, which subsequently decreases to about 440 mah g -1 after 15 cycles. As metallic cobalt is considered to be electrochemically inactive in these electrodes, the corresponding weight fraction was not considered when calculating the given capacity values. S11

12 Figure S9. The ex situ SEM micrographs of the CoS 2 -C/CNT anode for LIBs (a) after 60 cycles and (b) after 120 cycles. S12

13 Table S3. Comparison of the cycling performance of CoS 2 or CoS 2 -based composites, employed as active material for lithium-ion electrodes. Materials Compound Current density (ma g -1 ) Cycles Capacity (mah g -1 ) Ref. CoS2 or CoS2- based composite CoS2 composites including carbonaceous materials different from carbon nanotubes Carbonaceous CoS2 composite with carbon nanotubes CoS 2 Hollow Spheres CoS 2 NPs/Al 2 O 3 NSs Hierarchical Wormlike CoS The Yolk-shell CoS CoS 2 NPs/C CoS 2 -in-wall-ncss NC/CoS CoS 2 NP@G-CoS 2 QD NC@CoS CoS CoS 2 /G CoS 2 /G CoS 2 /graphene CoS 2 /rgo CNTs@C@CoS CoS 2 /fcnt CoS 2 /NCNTF CoS 2 /CNTs/graphene CoS 2 /GCAs CoS 2 /rgo/mwcnts This work CoS 2 -C/CNT S13

14 Table S4. Comparison of the rate capability of CoS 2 or CoS 2 -based composites, employed as active material for lithium-ion electrodes. Materials Compound Specific current (A g -1 ) Capacity (mah g -1 ) Ref. CoS2 or CoS2- based composite CoS 2 NPs/Al 2 O 3 NSs Hierarchical Worm-like CoS CoS 2 polyhedrons CoS2 composites including carbonaceous materials Carbonaceous CoS2 composite with carbon different from carbon nanotubes nanotubes CoS 2 NPs/C CoS 2 -in-wall-ncss NC/CoS CoS 2 NP@G-CoS 2 QD NC@CoS CoS CoS 2 /G CoS 2 /G CoS 2 /graphene CNTs@C@CoS CoS 2 /fcnt CoS 2 /NCNTF CoS 2 /CNTs/graphene CoS 2 /GCAs This work CoS 2 -C/CNT S14

15 Figure S10. CV curves recorded for electrodes based on CoS 2 -C/CNT vs. lithium metal at various scan rates ranging from 0.1 to 10.0 mv s -1. S15

16 Figure S11. Ex situ obtained (a) SEM and (b) TEM micrographs of the CoS 2 -C/CNT nanocomposite subjected to 200 dis-/charge cycles at a specific current of 100 ma g -1 in 1M NaPF 6 -DME vs. sodium metal. S16

17 Table S5. Comparison of the cycling performance of CoS 2 or CoS 2 -based composites, employed as active material for sodium-ion electrodes. Materials Compound Current density CoS2 CoS2 composites including carbonaceous materials different from carbon nanotubes (ma g -1 ) Cycles Capacity (mah g -1 ) Capacity retention (%) CoS ~30 35 Hollow CoS CoS 2 NPs/C CoS 2 /C polyhedrons Ref CoS 2 /rgo 100 ~ CoS CoS 2 /rgo Carbonaceous CoS2 composite with carbon nanotubes CoS 2 /GCAs CoS 2 -MWCNT This work 100 CoS 2 -C/CNT S17

18 Table S6. Comparison of the rate capability of CoS 2 or CoS 2 -based composites, employed as active material for sodium-ion electrodes. Materials Compound Specific current (A g -1 ) Capacity (mah g -1 ) Ref. CoS2 composites including CoS2 carbonaceous materials different Carbonaceous CoS2 composite with from carbon nanotubes carbon nanotubes CoS Hollow CoS CoS 2 NPs/C CoS 2 /C polyhedrons CoS 2 /rgo CoS CoS 2 /rgo CoS 2 /GCAs CoS 2 -MWCNT This work CoS 2 -C/CNT S18

19 References 1. Guo, Q.; Ma, Y.; Chen, T.; Xia, Q.; Yang, M.; Xia, H.; Yu, Y. Cobalt Sulfide Quantum Dot Embedded N/S-Doped Carbon Nanosheets with Superior Reversibility and Rate Capability for Sodium-Ion Batteries. ACS Nano 2017, 11, Xiao, Y.; Hwang, J.-Y.; Belharouak, I.; Sun, Y.-K. Superior Li/Na-Storage Capability of a Carbon-Free Hierarchical CoS x Hollow Nanostructure. Nano Energy 2017, 32, Fantauzzi, M.; Elsener, B.; Atzei, D.; Rigoldi, A.; Rossi, A. Exploiting XPS for the Identification of Sulfides and Polysulfides. RSC Adv. 2015, 5, Liu, S.; Wang, Z.; Zhou, S.; Yu, F.; Yu, M.; Chiang, C.-Y.; Zhou, W.; Zhao, J.; Qiu, J. Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution. Adv. Mater. 2017, 29, Zhao, Y.; Wang, L. P.; Sougrati, M. T.; Feng, Z.; Leconte, Y.; Fisher, A.; Srinivasan, M.; Xu, Z. A Review on Design Strategies for Carbon Based Metal Oxides and Sulfides Nanocomposites for High Performance Li and Na Ion Battery Anodes. Adv. Energy Mater. 2017, 7, Kan, J.; Wang, Y. Large and Fast Reversible Li-Ion Storages in Fe 2 O 3 -Graphene Sheeton-Sheet Sandwich-like Nanocomposites. Sci. Rep. 2013, 3, Zou, Y.; Wang, Y. NiO Nanosheets Grown on Graphene Nanosheets as Superior Anode Materials for Li-Ion Batteries. Nanoscale 2011, 3, Lu, L. Q.; Wang, Y. Sheet-like and Fusiform CuO Nanostructures Grown on Graphene by Rapid Microwave Heating for High Li-Ion Storage Capacities. J. Mater. Chem. 2011, 21, Chen, P.; Su, Y.; Liu, H.; Wang, Y. Interconnected Tin Disulfide Nanosheets Grown on Graphene for Li-Ion Storage and Photocatalytic Applications. ACS Appl. Mater. Interfaces 2013, 5, Geng, H.; Kong, S. F.; Wang, Y. NiS Nanorod-Assembled Nanoflowers Grown on Graphene: Morphology Evolution and Li-Ion Storage Applications. J. Mater. Chem. A 2014, 2, Ma, L.; Chen, W.-X.; Xu, L.-M.; Zhou, X.-P.; Jin, B. One-Pot Hydrothermal Synthesis of MoS 2 Nanosheets/C Hybrid Microspheres. Ceram. Int. 2012, 38, S19

20 12. Gu, Y.; Xu, Y.; Wang, Y. Graphene-Wrapped CoS Nanoparticles for High-Capacity Lithium-Ion Storage. ACS Appl. Mater. Interfaces 2013, 5, Peng, S.; Li, L.; Han, X.; Sun, W.; Srinivasan, M.; Mhaisalkar, S. G.; Cheng, F.; Yan, Q.; Chen, J.; Ramakrishna, S. Cobalt Sulfide Nanosheet/Graphene/Carbon Nanotube Nanocomposites as Flexible Electrodes for Hydrogen Evolution. Angew. Chem. Int. Ed. 2014, 53, Wang, Q.; Jiao, L.; Han, Y.; Du, H.; Peng, W.; Huan, Q.; Song, D.; Si, Y.; Wang, Y.; Yuan, H. CoS 2 Hollow Spheres: Fabrication and Their Application in Lithium-Ion Batteries. J. Phys. Chem. C 2011, 115, Fang, L.; Zhang, Y.; Guan, Y.; Zhang, H.; Wang, S.; Wang, Y. Specific Synthesis of CoS 2 Nanoparticles Embedded in Porous Al 2 O 3 Nanosheets for Efficient Hydrogen Evolution and Enhanced Lithium Storage. J. Mater. Chem. A 2017, 5, Jin, R.; Yang, L.; Li, G.; Chen, G. Hierarchical Worm-like CoS 2 Composed of Ultrathin Nanosheets as an Anode Material for Lithium-Ion Batteries. J. Mater. Chem. A 2015, 3, Qiu, W.; Jiao, J.; Xia, J.; Zhong, H.; Chen, L. A Self-Standing and Flexible Electrode of Yolk-Shell CoS 2 Spheres Encapsulated with Nitrogen-Doped Graphene for High- Performance Lithium-Ion Batteries. Chem. - Eur. J. 2015, 21, Zhang, Y.; Wang, N.; Sun, C.; Lu, Z.; Xue, P.; Tang, B.; Bai, Z.; Dou, S. 3D Spongy CoS 2 Nanoparticles/Carbon Composite as High-Performance Anode Material for Lithium/Sodium Ion Batteries. Chem. Eng. J. 2018, 332, Xia, H.; Li, K.; Guo, Y.; Guo, J.; Xu, Q.; Zhang, J. CoS 2 Nanodots Trapped within Graphitic Structured N-Doped Carbon Spheres with Efficient Performances for Lithium Storage. J. Mater. Chem. A 2018, 6, Wang, Q.; Zou, R.; Xia, W.; Ma, J.; Qiu, B.; Mahmood, A.; Zhao, R.; Yang, Y.; Xia, D.; 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, He, J.; Chen, Y.; Li, P.; Fu, F.; Wang, Z.; Zhang, W. Self-Assembled CoS 2 Nanoparticles Wrapped by CoS 2 -Quantum-Dots-Anchored Graphene Nanosheets as Superior- Capability Anode for Lithium-Ion Batteries. Electrochim. Acta 2015, 182, S20

21 22. Peng, S.; Li, L.; Mhaisalkar, S. G.; Srinivasan, M.; Ramakrishna, S.; Yan, Q. Hollow Nanospheres Constructed by CoS 2 Nanosheets with a Nitrogen-Doped-Carbon Coating for Energy-Storage and Photocatalysis. ChemSusChem 2014, 7, Chen, W.; Li, T.; Hu, Q.; Li, C.; Guo, H. Hierarchical CoS Hollow Microspheres Constructed by Nanosheets with Superior Lithium Storage. J. Power Sources 2015, 286, Tao, S.; Huang, W.; Xie, H.; Zhang, J.; Wang, Z.; Chu, W.; Qian, B.; Song, L. Formation of Graphene-Encapsulated CoS 2 Hybrid Composites with Hierarchical Structures for High-Performance Lithium-Ion Batteries. RSC Adv. 2017, 7, Guo, J.; Li, F.; Sun, Y.; Zhang, X.; Tang, L. Graphene-Encapsulated Cobalt Sulfides Nanocages with Excellent Anode Performances for Lithium Ion Batteries. Electrochim. Acta 2015, 167, Xie, J.; Liu, S.; Cao, G.; Zhu, T.; Zhao, X. Self-Assembly of CoS 2 /Graphene Nanoarchitecture by a Facile One-Pot Route and Its Improved Electrochemical Li- Storage Properties. Nano Energy 2013, 2, Su, Q.; Xie, J.; Zhang, J.; Zhong, Y.; Du, G.; Xu, B. In Situ Transmission Electron Microscopy Observation of Electrochemical Behavior of CoS 2 in Lithium-Ion Battery. ACS Appl. Mater. Interfaces 2014, 6, Jin, R.; Zhai, Q.; Wang, Q. Amorphous Transition Metal Sulfides Anchored on Amorphous Carbon-Coated Multiwalled Carbon Nanotubes for Enhanced Lithium-Ion Storage. Chem. - Eur. J. 2017, 23, Huang, Z. X.; Wang, Y.; Wong, J. I.; Shi, W. H.; Yang, H. Y. Synthesis of Self- Assembled Cobalt Sulphide Coated Carbon Nanotube and Its Superior Electrochemical Performance as Anodes for Li-Ion Batteries. Electrochim. Acta 2015, 167, Zhang, J.; Yu, L.; Lou, X. W. D. Embedding CoS 2 Nanoparticles in N-Doped Carbon Nanotube Hollow Frameworks for Enhanced Lithium Storage Properties. Nano Res. 2017, 10, Xu, C.; Jing, Y.; He, J.; Zhou, K.; Chen, Y.; Li, Q.; Lin, J.; Zhang, W. Self-Assembled Interwoven CoS 2 /CNTs/Graphene Architecture as Anode for High-Performance Lithium Ion Batteries. J. Alloys Compd. 2017, 708, S21

22 32. Zhang, X.; Jie Liu, X.; Wang, G.; Wang, H. Cobalt Disulfide Nanoparticles/Graphene/Carbon Nanotubes Aerogels with Superior Performance for Lithium and Sodium Storage. J. Colloid Interface Sci. 2017, 505, Zhu, X.; Meng, Z.; Ying, H.; Xu, X.; Xu, F.; Han, W. A Novel CoS 2 /Reduced Graphene Oxide/Multiwall Carbon Nanotubes Composite as Cathode for High Performance Lithium Ion Battery. Chem. Phys. Lett. 2017, 684, Wang, Y.; Wu, J.; Tang, Y.; Lü, X.; Yang, C.; Qin, M.; Huang, F.; Li, X.; Zhang, X. Phase-Controlled Synthesis of Cobalt Sulfides for Lithium Ion Batteries. ACS Appl. Mater. Interfaces 2012, 4, Shadike, Z.; Cao, M.-H.; Ding, F.; Sang, L.; Fu, Z.-W. Improved Electrochemical Performance of CoS 2 MWCNT Nanocomposites for Sodium-Ion Batteries. Chem. Commun. 2015, 51, Liu, X.; Zhang, K.; Lei, K.; Li, F.; Tao, Z.; Chen, J. Facile Synthesis and Electrochemical Sodium Storage of CoS 2 Micro/Nano-Structures. Nano Res. 2016, 9, Han, F.; Lv, T.; Sun, B.; Tang, W.; Zhang, C.; Li, X. In Situ Formation of Ultrafine CoS 2 Nanoparticles Uniformly Encapsulated in N/S-Doped Carbon Polyhedron for Advanced Sodium-Ion Batteries. RSC Adv. 2017, 7, Xie, K.; Li, L.; Deng, X.; Zhou, W.; Shao, Z. A Strongly Coupled CoS 2 /Reduced Graphene Oxide Nanostructure as an Anode Material for Efficient Sodium-Ion Batteries. J. Alloys Compd. 2017, 726, Pan, Y.; Cheng, X.; Huang, Y.; Gong, L.; Zhang, H. CoS 2 Nanoparticles Wrapping on Flexible Freestanding Multichannel Carbon Nanofibers with High Performance for Na- Ion Batteries. ACS Appl. Mater. Interfaces 2017, 9, Li, Z.; Feng, W.; Lin, Y.; Liu, X.; Fei, H. Flaky CoS 2 and Graphene Nanocomposite Anode Materials for Sodium-Ion Batteries with Improved Performance. RSC Adv. 2016, 6, S22