An Alternative Anode for Full-Cell Li-Ion and Na ... - ACS Publications

Subscriber access provided by Kaohsiung Medical University

Functional Nanostructured Materials (including low-D carbon)

One-dimensional Integrated MnS@Carbon Nanoreactors Hybrid: An Alternative Anode for Full-cell Li-ion and Na-ion Batteries Yani Liu, Linpo Li, Jianhui Zhu, Ting Meng, Lai Ma, Han Zhang, Maowen Xu, Jian Jiang, and Chang Ming Li ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.8b05688 • Publication Date (Web): 24 Jul 2018 Downloaded from http://pubs.acs.org on July 25, 2018

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 32 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Applied Materials & Interfaces

One-dimensional

Integrated

MnS@Carbon

Nanoreactors

Hybrid: An Alternative Anode for Full-cell Li-ion and Na-ion Batteries Yani Liu,a,c Linpo Li,

a,c

Jianhui Zhu,b Ting Meng, a,c Lai Ma, a,c Han Zhang, a,c Maowen Xu, a,c

Jian Jiang,a,c* Chang Ming Lia,c* a

Institute for Clean Energy & Advanced Materials, Faculty of Materials and Energy, Southwest

University, No.2 Tiansheng Road, Chongqing 400715, P.R. China. b

School of Physical Science and Technology, Southwest University, No.2 Tiansheng Road,

Chongqing 400715, P.R. China. c

Chongqing Key Laboratory for Advanced Materials and Technologies of Clean Energies, No.2

Tiansheng Road, Chongqing 400715, P.R. China. *

E-mail: [email protected] (C.M.Li); [email protected] (J. Jiang).

Abstract: The manganese sulfide (MnS) has triggered great interest as an anode material for rechargeable Li-ion/Na-ion batteries (LIBs/SIBs) due to its low cost, high electrochemical activity and theoretical capacity. Nevertheless, the practical application is greatly hindered by its rapid capacity decay leading by inevitable actives dissolution and volume expansions in charge/discharge cycles. To settle above issues in LIBs/SIBs, we herein put forward the smart construction of MnS nanowires embedded in carbon nanoreactors (MnS@C NWs) via a facile solution method followed by a scalable in-situ sulfuration treatment. This engineering protocol toward electrode architectures/ configurations endows integrated MnS@C NWs anodes with large specific capacity (with a Max. value of 847 mAh g-1 in LIBs and 720 mAh g-1 in SIBs), good operation stability, excellent rate capabilities and prolonged cyclic lifespan. To prove their potential real applications, we have

ACS Paragon Plus Environment

ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

established the full cells (for LIBs: MnS@C//LiFePO4; for SIBs: MnS@C//Na3V2(PO4)3), both of which are capable to show remarkable specific capacities, outstanding rate performance and superb cyclic endurance. This work offers a scalable, simple and efficient evolution way to produce the integrated hybrid of MnS@C NWs, providing useful inspiration/guideline for anodic applications of metal sulfides in next-generation power sources.

Keywords: MnS@C NWs; in-situ sulfuration; anodes; LIBs/SIBs; full cells


Page 2 of 32

Page 3 of 32 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Introduction There has been a strong increase in the demand for high-energy density and long-lasting rechargeable batteries for wide practical applications, particularly like grid-scale energy storage and electric vehicles.1-2 Li-ion batteries (LIBs) and Na-ion batteries (SIBs) are both considered as the most promising candidates due to their high energy density, long lifespan and good environmental benignity when compared to counterparts like Ni-MH batteries, Ni-Zn batteries, lead-acid batteries and supercapacitors, etc.3-5 Generally, the LIBs/SIBs performance is tight associated with the properties of electrode materials.6-7 Recently, transition metal sulfides (e.g., MoS2, FeS2, Co9S8, SnS2, VS2, MnS, etc.) have triggered tremendous attention as anodes owing to their low expenditure, unique physical and chemical properties (e.g., higher electrical conductivity, mechanical stability and electrochemical activity than those of their corresponding metal oxides) and impressive theoretical capacity.8-12 Among them, MnS, a p-type semiconductor with a wide band gap (Eg=3.7 eV), has been studied as a promising electrode candidate for LIBs/SIBs due to its great natural abundance, eco-friendliness and high theoretical capacity (616 mAh g-1 according to the electromotive force of 1.049 V and Gibbs free energy change of -202.50 kJ mol-1).13-17 Unfortunately, for MnS anode species, there still exist several obstacles in the way to practical applications. First, the intrinsically insulating property of MnS is a major impediment, leading to electrochemical reactions sluggish and poor rate capacibility of LIBs/SIBs.18 Second, inevitable volume expansions and phase changes in Li+/Na+ insertion/extraction processes would induce the negative agglomerations of electrode materials and thus a rapid capacity decay.19 Particularly, Na+ (~0.102 nm) inherently possesses a larger radius than Li+ (~0.076 nm), which inevitably results in more severe volume changes and inferior capacity retention/cyclic stability of MnS for SIBs



application. Besides, the dissolutions/losses of polysulfide intermediates (formed in battery charging) would further accelerate the capacity degradation and meantime deteriorate the Coulombic efficiency (CE).20-21 Third, the mainstream MnS fabrication usually relies on the use of hazardous chemical reagents (e.g., Na2S and N2H4·H2O).14-16 Moreover, the diameter for as-made MnS products is quite bulky (above 1 µm per unit in most cases);14-16 such a huge size renders a long ionic diffusion distance in Li+/Na+ intercalation/deintercalation, which is unbeneficial for energy-storage usage.22 In an attempt to mitigate problems aforementioned, downsizing MnS actives into the nanoscale is regarded as a feasible and effective way.23-26 Though using this strategy may well improve the electrode kinetics since nanoparticles ( 2.5 V; rated power: 3 W) with a lighting duration time over 5 min, which makes them hold a great promise in both peak-power and energy supply applications. In parallel, for SIBs applications, full cells of MnS@C//NVP are further assembled and studied (see the schematic in the inset of Figure 6a). Figure 6a displays the CV plots of MnS@C//NVP in a voltage range of 1.5-4 V at 0.5 mV s-1. As noted, this CV profile inherits the electrochemical characteristics of both anode and cathode, showing an evident reduction peak in the voltage of ~2.2-2.6 V and an oxidant peak within ~2.8-3.5 V. The related cell reactions are listed as follows: Anode: MnS + 2Na + 2e ↔ Mn + Na S (6) Cathode: Na V (PO) ) ↔ Na( х) V (PO) ) + хNa + хe (7) The full cells are measured by galvanostatic charge/discharge tests (See their charge/discharge profiles in Figure 6b). Except for the initial case, the sloped plateaus (for charge: ~2.58-2.85 V; for discharge: ~2.05-2.68 V) over all cycles (from the 1st to 200th) are nearly the same with each other, reflecting the good electrochemical reversibility and cyclic stability of MnS@C//NVP. The cyclic endurance and rate performance are recorded in Figure 6c. After 180 cycles at 0.1 A g-1, the delivered discharge capacity still retains ~83 mAh g-1, ~89% of the value for the 2nd cycle (~95 mAh g-1), indicative of excellent long-time cyclic behaviors. When suffering from current variations, the full cells of MnS@C//NVP can output a specific capacity of 80 mAh g-1 (0.1 A g-1), 73 mAh g-1 (0.25 A g-1), 64 mAh g-1 (0.5 A g-1), 55 mAh g-1 (1 A g-1) and 47 mAh g-1 (2 A g-1), respectively. Even once the current rises by 40 times (from 0.1 A g-1) to 4 A g-1, this full cell still remains a capacity of ~40 mAh g-1. The EIS spectrum (in the inset of Figure 6c) reveals the good cell kinetics of MnS@C//NVP due to small differences before and after long-term cyclic testing. Also, to prove


Page 16 of 32

Page 17 of 32 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


their potential for practical usage, a single full cell can drive a green LED light (see Figure 6c; working voltage: above 2.5 V; rated power: ~0.5 W).

Conclusions In summary, the fabrication of MnS@C hybrid NWs is realized by combining the solution method and the in-situ sulfuration treatment towards raw materials of MnO2 NWs. The outer C matrix can effectively buffer the volume changes and improve the structural stability of electrodes, leading to the improvement on cyclic lifetime and rate capability. Thanks to such unique structural features, the as-made hybrid anode of MnS@C NWs exhibits high reversible capacities (847 mAh g-1 at 0.1 A g-1 in LIBs and 540 mAh g-1 at 0.02 A g-1 in SIBs), outstanding rate performance and cyclic stability in both LIBs and SIBs. To demonstrate its potential practical usage, full-cell devices of MnS@C//LiFePO4 and MnS@C//NVP are further developed. Such devices can successfully drive LEDs, holding a good promise in applications for portable electronic devices. Our work not only provides a convenient, efficient and general synthetic method to produce integrated sulfides within C matrix, but also demonstrates their great potential in full-cell LIBs and SIBs applications.

Supporting Information for Publication available: Thermogravimetric analysis (TGA) result of MnS@C NWs; TEM/SEM observations and EDS elemental mapping of cycled MnS@C NWs electrodes for both LIBs and SIBs.

Acknowledgment: We gratefully acknowledge financial support from Fundamental Research Funds for the Central Universities (SWU 115027, SWU 115029, XDJK2018C005), the National Natural Science Foundation of China (11604267) and Chongqing Natural Science Foundation



(cstc2016jcyjA0477). This project is also supported by Program for Innovation Team Building at Institutions of Higher Education in Chongqing (CXTDX201601011, XDJK2017A002).

References 1. Ren, W.; Yao, X.; Niu, C.; Zheng, Z.; Zhao, K.; An, Q.; Wei, Q.; Yan, M.; Zhang, L.; Mai, L. Cathodic Polarization Suppressed Sodium-Ion Full Cell with a 3.3 V High-Voltage. Nano Energy 2016, 28, 216-223.

2. Mohana Reddy, A. L.; Gowda, S. R.; Sh aijumon, M. M.; Ajayan, P. M. Hybrid Nanostructures for Energy Storage Applications. Adv. Mater. 2012, 24, 5045-5064.

3. He, X.; Li, J.; Cheng, H.; Jiang, C.; Wan, C. Controlled Crystallization and Granulation of Nano-Scale β-Ni(OH)2 Cathode Materials for High Power Ni-MH Batteries. J. Power Sources 2005, 152, 285-290.

4. Huang, J.; Yang, Z.; Wang, T. Evaluation of Tetraphenylporphyrin Modified ZnO as Anode Material for Ni-Zn Rechargeable Battery. Electrochim. Acta 2014, 123, 278-284.

5. Banerjee, A.; Ziv, B.; Shilina, Y.; Levi, E.; Luski, S.; Aurbach, D. Single-Wall Carbon Nanotube Doping in Lead-Acid Batteries: A New Horizon. ACS Appl. Mater. Interfaces 2017, 9, 3634-3643.

6. Hu, Z.; Liu, Q.; Chou, S.-L.; Dou, S.-X. Advances and Challenges in Metal Sulfides/Selenides for Next-Generation Rechargeable Sodium-Ion Batteries. Adv. Mater. 2017, 29, 1700606.


Page 18 of 32

Page 19 of 32 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


7. Tan, R.; Yang, J.; Hu, J.; Wang, K.; Zhao, Y.; Pan, F. Core-Shell Nano-FeS2@N-Doped Graphene as an Advanced Cathode Material for Rechargeable Li-Ion Batteries. Chem. Commun. 2016, 52, 986-989.

8. Zhu, C.; Mu, X.; van Aken, P. A.; Yu, Y.; Maier, J. Single-Layered Ultrasmall Nanoplates of MoS2 Embedded in Carbon Nanofibers with Excellent Electrochemical Performance for Lithium and Sodium storage. Angew. Chem. 2014, 53, 2152-2156.

9. Zhan, J.; Deng, S.; Zhong, Y.; Wang, Y.; Wang, X.; Yu, Y.; Xia, X.; Tu, J. Exploring Hydrogen Molybdenum Bronze for Sodium Ion Storage: Performance Enhancement by Vertical Graphene Core and Conductive Polymer Shell. Nano Energy 2018, 44, 265-271.

10. Zhu, Y.; Fan, X.; Suo, L.; Luo, C.; Gao, T.; Wang, C. Electrospun FeS2@Carbon Fiber Electrode as a High Energy Density Cathode for Rechargeable Lithium Batteries. ACS Nano 2016, 10, 1529-1538.

11. Song, X.; Li, X.; Bai, Z.; Yan, B.; Li, D.; Sun, X. Morphology-Dependent Performance of Nanostructured Ni3S2/Ni Anode Electrodes for High Performance Sodium Ion Batteries. Nano Energy 2016, 26, 533-540.

12. Qu, B.; Ma, C.; Ji, G.; Xu, C.; Xu, J.; Meng, Y. S.; Wang, T.; Lee, J. Y. Layered SnS2-Rreduced Graphene Oxide Composite-a High-Capacity, High-Rate, and Long-Cycle Life Sodium-Ion Battery Anode Material. Adv. Mater. 2014, 26, 3854-3859.



13. Sun, R.; Wei, Q.; Sheng, J.; Shi, C.; An, Q.; Liu, S.; Mai, L. Novel Layer-by-Layer Stacked VS2 Nanosheets with Intercalation Pseudocapacitance for High-Rate Sodium Ion Charge Storage. Nano Energy 2017, 35, 396-404.

14. Deng, S.; Chao, D.; Zhong, Y.; Zeng, Y.; Yao, Z.; Zhan, J.; Wang, Y.; Wang, X.; Lu, X.; Xia, X.; Tu, J. Vertical Graphene/Ti2Nb10O29/Hydrogen Molybdenum Bronze Composite Arrays for Enhanced Lithium Ion Storage. Energy Storage Mater. 2018, 12, 137-144.

15. Wang, D.; Xia, X.; Wang, Y.; Xie, D.; Zhong, Y.; Wu, J.; Wang, X.; Tu, J. Vertical-Aligned Li2S-Graphene Encapsulated within a Carbon Shell as a Free-Standing Cathode for Lithium-Sulfur Batteries. Chem. Eur. J. 2017, 23, 11169-11174.

16. Wu, C.; Maier, J.; Yu, Y. Generalizable Synthesis of Metal-Sulfides/Carbon Hybrids with Multiscale, Hierarchically Ordered Structures as Advanced Electrodes for Lithium Storage. Adv. Mater. 2016, 28, 174-180.

17. Xu, X.; Ji, S.; Gu, M.; Liu, J. In Situ Synthesis of MnS Hollow Microspheres on Reduced Graphene Oxide Sheets as High-Capacity and Long-Life Anodes for Li- and Na-Ion Batteries. ACS Appl. Mater. Interfaces 2015, 7, 20957-20964.

18. Rui, X.; Tan, H.; Yan, Q. Nanostructured Metal Sulfides for Energy Storage. Nanoscale 2014, 6, 9889-9924.

19. Ning, J.; Zhang, D.; Song, H.; Chen, X.; Zhou, J. Branched Carbon-Encapsulated MnS Core/Shell Nanochains Prepared via Oriented Attachment for Lithium-ion Storage. J. Mater. Chem. A 2016, 4, 12098-12105.


Page 20 of 32

Page 21 of 32 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


20. Jiang, J.; Li, L.; Xu, M.; Zhu, J.; Li, C. M. In Situ Packaging FeFx into Sack-like Carbon Nanoreactors: A Smart Way to Make Soluble Fluorides Applicable to Aqueous Batteries. ACS Appl. Mater. Interfaces 2016, 8, 3874-3882.

21. Xie, D.; Xia, X.; Zhong, Y.; Wang, Y.; Wang, D.; Wang, X.; Tu, J. Exploring Advanced Sandwiched Arrays by Vertical Graphene and N-Doped Carbon for Enhanced Sodium Storage. Adv. Energy Mater. 2017, 7, 1601804.

22. Liu, P.; Hao, Q.; Xia, X.; Lei, W.; Xia, H.; Chen, Z.; Wang, X. Hollow Amorphous MnSnO3 Nanohybrid with Nitrogen-Doped Graphene for High-Performance Lithium Storage. Electrochim. Acta 2016, 214, 1-10.

23. Darwiche, A.; Marino, C.; Sougrati, M. T.; Fraisse, B.; Stievano, L.; Monconduit, L. Better Cycling Performances of Bulk Sb in Na-Ion Batteries Compared to Li-Ion Systems: an Unexpected Electrochemical Mechanism. J. Am. Chem. Soc. 2012, 134, 20805-20811.

24. Zhong, Y.; Chao, D.; Deng, S.; Zhan, J.; Fang, R.; Xia, Y.; Wang, Y.; Wang, X.; Xia, X.; Tu, J. Confining Sulfur in Integrated Composite Scaffold with Highly Porous Carbon Fibres/Vanadium Nitride Arrays for High-performance Lithium-Sulfur Batteries Adv. Funct. Mater. 2018, 1706391.

25. Deng, S.; Zhong, Y.; Zeng, Y.; Wang, Y.; Yao, Z.; Yang, F.; Lin, S.; Wang, X.; Lu, X.; Xia, X.; Tu, J. Directional Construction of Vertical Nitrogen doped 1T-2H MoSe2/Graphene Shell/Core Nanoflake Arrays for Efficient Hydrogen Evolution Reaction. Adv. Mater. 2017, 29, 1700748.



26. Jiang, J.; Li, L.; Xu, M.; Zhu, J.; Li, C. M. FeF3@Thin Nickel Ammine Nitrate Matrix: Smart Configurations and Applications as Superior Cathodes for Li-Ion Batteries. ACS Appl. Mater. Interfaces 2016, 8, 16240-16247.

27. He, M.; Kravchyk, K.; Walter, M.; Kovalenko, M. V. Monodisperse Antimony Nanocrystals for High-Rate Li-Ion and Na-Ion Battery Anodes: Nano Versus Bulk. Nano Lett. 2014, 14, 1255-1262.

28. Chen, G.; Yan, L.; Luo, H.; Guo, S. Nanoscale Engineering of Heterostructured Anode Materials for Boosting Lithium-Ion Storage. Adv. Mater. 2016, 28, 7580602.

29. Wang, Y.; Yu, L.; Lou, X. W. Formation of Triple-Shelled Molybdenum-Polydopamine Hollow Spheres and Their Conversion into MoO2/Carbon Composite Hollow Spheres for Lithium-Ion Batteries. Angew. Chem. 2016, 55, 14668-14672.

30. Wang, K. X.; Li, X. H.; Chen, J. S. Surface and Interface Engineering of Electrode Materials for Lithium-ion Batteries. Adv. Mater. 2015, 27, 527-545.

31. Sun, T.; Li, Z.; Wang, H.; Bao, D.; Meng, F.; Zhang, X. A Biodegradable Polydopamine-Derived Electrode Material for High-Capacity and Long-Life Lithium-Ion and Sodium-Ion Batteries. Angew. Chem. 2016, 128, 10820-10824.

32. Mai, L.; Tian, X.; Xu, X.; Chang, L.; Xu, L. Nanowire Electrodes for Electrochemical Energy Storage Devices. Chem. Rev. 2014, 114, 11828-11862.


Page 22 of 32

Page 23 of 32 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


33. Zhong, Y.; Xia, X. H.; Deng, S. J.; Zhan, J. Y.; Fang, R. Y.; Xia, Y.; Wang, X. L.; Zhang, Q.; Tu, J. P. Popcorn Inspired Porous Macrocellular Carbon: Rapid Puffing Fabrication from Rice and Its Applications in Lithium–Sulfur Batteries. Adv. Energy Mater. 2018, 8, 1701110.

34. Li, L.; Zhu, J.; Niu, Y.; Chen, Z.; Liu, Y.; Liu, S.; Xu, M.; Li, C. M.; Jiang, J. Efficient Production of Coaxial Core–Shell MnO@Carbon Nanopipes for Sustainable Electrochemical Energy Storage Applications. ACS Sustainable Chem. Eng. 2017, 5, 6288-6296.

35. Jiang, H.; Hu, y.; Guo, S.; Yan, C.; Lee, P.; Li, C. Rational Design of MnO/Carbon Nanopeapods with Internal Void Space for High-Rate and Long-Life Li-Ion Batteries. ACS nano 2014, 8, 6038-6046.

36. Xu, X.; Liu, J.; Liu, Z.; Shen, J.; Hu, R.; Liu, J.; Ouyang, L.; Zhang, L.; Zhu, M. Robust Pitaya-Structured Pyrite as High Energy Density Cathode for High-Rate Lithium Batteries. ACS Nano 2017, 11, 9033-9040.

37. Shi, L.; Pang, C.; Chen, S.; Wang, M.; Wang, K.; Tan, Z.; Gao, P.; Ren, J.; Huang, Y.; Peng, H.; Liu, Z. Vertical Graphene Growth on SiO Microparticles for Stable Lithium Ion Battery Anodes. Nano Lett. 2017, 17, 3681-3687.

38. Wang, J.-G.; Jin, D.; Liu, H.; Zhang, C.; Zhou, R.; Shen, C.; Xie, K.; Wei, B. All-Manganese-Based Li-ion Batteries with High Rate Capability and Ultralong Cycle Life. Nano Energy 2016, 22, 524-532.



39. Liu, J.; Jiang, J.; Cheng, C.; Li, H.; Zhang, J.; Gong, H.; Fan, H. J. Co3O4 Nanowire@MnO2 Ultrathin Nanosheet Core/Shell Arrays: A New Class of High-Performance Pseudocapacitive Materials. Adv. Mater. 2011, 23, 2076-2081.

40. Wang, J.-G.; Liu, H.; Liu, H.; Fu, Z.; Nan, D. Facile Synthesis of Microsized MnO/C Composites With High Tap Density as High Performance Anodes for Li-ion Batteries. Chem. Eng. J. 2017, 328, 591-598.

41. Xia, X.; Zhu, C.; Luo, J.; Zeng, Z.; Guan, C.; Ng, C. F.; Zhang, H.; Fan, H. J. Synthesis of Free-Standing Metal Sulfide Nanoarrays via Anion Exchange Reaction and their Electrochemical Energy Storage Application. Small 2014, 10, 766-773.


Page 24 of 32

Page 25 of 32 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure Captions:

Figure 1. (a) General schematic showing the overall evolution of MnS@C NWs. (b-d) SEM observations and (e) XRD patterns of samples at distinct evolution stages: (b) MnO2 NWs precursors, (c) MnO@C NWs intermediates and (d) MnS@C NWs. (f-g) TEM observations on the ultimate hybrids of MnS@C NWs.

Figure 2. (a) EDS spectrum, (b-e) elemental mappings, and (f) Raman spectrum of MnS@C NWs. (g-i) XPS detecting toward MnS@C NWs: (g) Mn 2p spectrum, (h) C 1s and (i) S 2p spectrum.

Figure 3. (a) CV curves, (b) programmed cyclic records, (c) charge/discharge profiles, (d) specific capacity vs. current density plot and (e) EIS spectra of MnS@C NWs for Li storage.

Figure 4. (a) CV curves, (b) programmed cyclic records, (c) charge/discharge profiles, (d) specific capacity vs. current density plot and (e) EIS spectra of MnS@C NWs for Na storage.

Figure 5. (a) CV curves, (b) charge−discharge profiles at a current density of 0.1 A g-1 and (c) programmed cyclic records of MnS@C//LiFePO4 full cells (Inset: EIS spectra and optical image displaying a single cell can drive a high-power blue LED light).

Figure 6. (a) CV curves, (b) charge−discharge profiles at a current density of 0.1 A g-1 and (c) programmed cyclic records of MnS@C//NVP full cells (Inset: EIS spectra and optical image showing a single cell can drive a green LED light).



a Sulfuration

Polymerization Carbonization

b

MnO@C NWs

c

MnO2 NWs

100 nm

e Intensity (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41

Page 26 of 32

(200)

(220) (222)

(200) (111)

100 nm

100 nm

MnS JPCDS Card No. 88-2223

(111)

MnS@C NWs

d

g

f

(400)

MnS

MnO JPCDS Card No. 89-2804

0.3 nm (111)

(220) (311)(222)

0.18 nm (110) (200)

(220)

MnO2 JPCDS Card No. 72-1982

(310) (400)

(121)

(411) (301) (510)

(600)

10 nm

20 nm 10

20

30

40

50

2 Theta

60

70

80

Figure 1 ACS Paragon Plus Environment

a

c

b

Mn

Intensity (a.u.)

Cu (Background) 100 nm

d C Mn 0.6

1.2

1.8

Energy (eV)

2.4

S

3.0

600

h

800

1000

1200

G band

1400

655

Binding Energy (eV)

660

i

C 1s

Intensity (a.u.)

Mn 2p1/2

650

D band

1600

Raman Shift (cm )

Mn 2p3/2

645

MnS

-1

Mn 2p

640

e

S

g

635

C

f

C-C C=C C-O

280

282

284

286

288

Binding Energy (eV)


290

S 2p

S 2p3/2

Intensity (a.u.)

0.0

Intensity (a.u.)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41


Intensity (a.u.)

Page 27 of 32

292

S 2p1/2

SOX

160

162

164

Binding Energy (eV)

166

1800


a

b

0.1 A g-1

10th

5th

MnS@C NWs

0.1 A g-1

1st

2nd Bare MnS NWs

c

d

200

3.0

+

Potential (V vs. Li/Li )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41

Page 28 of 32

2.5

0.5A g-1

50

500

2.0

e

0.1 A g-1

1 A g-1

100

2 A g-1

4 A g-1

1.5

6 A g-1 After Cycling

1.0

1 0.5 0.0

Before Cycling 0

200

400

600

800

1000

1200

1400

-1

Capacity (mAh g )


Page 29 of 32

b -1

Capacity (mAh g )

5th

3rd

1st

1200 100 1000 80

800

60

600

0.02 A g-1

MnS@C NWs

0.02 A g-1 40

400

20

200

Bare MnS NWs

0

0

50

100

150

200

250

300

350

Cycle number

c

d 500

150

Capacity (mAh g )

+

3.0

-1

200

2.4

50 100

1.8 1.2

1 0.6 0.0

0

100

200

300

400

500

600 -1

Capacity (mAh g )

700

400

0.02 A g-1 0.5 A g-1 1 A g-1

e 2 A g-1

3 A g-1 4 A g-1

300

After Cycling 200 100 0

Before Cycling 0

1

2

3

-1

Current Density (A g )


4

400

0

Coulombic efficiency (%)

a

Potential (V vs. Na/Na )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41



3 LiFePO4 Cathode

2

Current (A)

b

2nd Li+

1

1st

MnS@C Hybrid NWs

0

5th

-1 -2

10th 2.0

2.5

3.0

4.2

200 100

3.6

Separator

Voltage (V)

a

3.5

1

50

3.0 2.4 1.8 1.2

0.5 mV s-1 4.0

300

500

0

4.5

30

60

90

120

-1

150

Capacity (mAh g )

Potential (V)

100

150

80

0.1 A g-1

120 90

-Z'' (ohm)

-1

180

60 30

0.1 A g-1

40

40

After Cycling 20

20

Before Cycling 0

0

20

0 0

60

100

40

60

80

Z' (ohm)

100

0 200

300

Cycle Number

Figure 5


400

500

600


c Capacity (mAh g )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41

Page 30 of 32

Page 31 of 32

0.15

Separator

5th

0.05

MnS@C Hybrid NWs

0.00 -0.05

2nd 1.5

120

100 50

20

1

3.5 3.0 2.5

2.0

2.5

3.0

0.2 mV s-1 3.5

4.0

1.5

0

20

40

60

80

-1

100

Capacity (mAh g )

Potential (V)

100 80

0.1 A g-1

90 60 30

-Z'' (ohm)

-1

150

150 200

2.0

-0.10

c

b 4.0

0

60

100

40 After Cycling

50

20 0

0

0.1 A g-1

Before Cycling

0

100

200

300

Z' (ohm)

50

100

150

Cycle Number


200

250

0


Current (mA)

0.10

1st

Na+

NVP Cathode

Voltage (V)

a

Capacity (mAh g )

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41


ACS Applied Materials & Interfaces 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41

Page 32 of 32

PDA Coating Sulfuration

(-)MnS@C//LiFePO4(+)

(-)MnS@C//NVP(+)

SIBs

LIBs


An Alternative Anode for Full-Cell Li-Ion and Na ... - ACS Publications

Recommend Documents