logo

Sulfur/nickel ferrite composite as cathode with high-volumetric-capacity for lithium-sulfur battery

More info
  • ReceivedMar 28, 2018
  • AcceptedApr 29, 2018
  • PublishedJun 1, 2018

Abstract

Low volumetric energy density is a bottleneck for the application of lithium-sulfur (Li-S) battery. The low-density sulfur cooperated with the light-weight carbon substrate realizes electrochemical cycle stability, but leads to worse volumetric energy density. Here, nickel ferrite (NiFe2O4) nanofibers as novel substrate for sulfur not only anchor lithium polysulfides to enhance the cycle stability of sulfur cathode, but also contribute to the high volumetric capacity of the S/nickel ferrite composite. Specifically, the S/nickel ferrite composite presents an initial volumetric capacity of 1,281.7 mA h cm−3-composite at 0.1 C rate, 1.9 times higher than that of S/carbon nanotubes, due to the high tap density of the S/nickel ferrite composite.


Funded by

This work is financially supported from the New Energy Project for Electric Vehicles in National Key Research and Development Program(2016YFB0100200)

the National Natural Science Foundation of China(21573114,51502145)


Acknowledgment

This work is financially supported by the New Energy Project for Electric Vehicles in National Key Research and Development Program (2016YFB0100200) and the National Natural Science Foundation of China (21573114 and 51502145)


Interest statement

The authors declare no conflict of interest.


Contributions statement

Zhang Z, and Gao XP conceived the idea. Zhang Z carried out the preparation and electrochemical tests of the composites. Zhou Z and Wu DH performed the computational experiments. Liu S and Li GR contributed to the impedance analysis. Zhang Z, and Gao XP co-wrote the paper. All the authors contributed to the general discussion.


Author information

Ze Zhang is a Lecturer in the School of Chemistry, Nanchang University. He received his BS degree in 2012 from the College of Chemistry, and PhD degree in 2017 from the School of Materials Science and Engineering, Nankai University of China. His general research interest is in the area of advanced functional materials for rechargeable batteries with a focus on the exploration of high-energy Li-S battery.


Xue-Ping Gao is a Professor in the Institute of New Energy Material Chemistry, Nankai University, China. He received his doctorate at the Department of Chemistry from Nankai University in 1995. He used to work as a visiting research fellow at Kogakuin University in Japan from 1997 to 1999. Currently, his main research focuses on energy storage materials for power sources, including Li-ion batteries, Li-S battery and solar rechargeable battery.


Supplement

Supplementary information

Supporting data are available in the online version of the paper.


References

[1] Bruce PG, Freunberger SA, Hardwick LJ, et al. Li–O2 and Li–S batteries with high energy storage. Nat Mater, 2012, 11: 19-29 CrossRef PubMed ADS Google Scholar

[2] Gao XP, Yang HX. Multi-electron reaction materials for high energy density batteries. Energy Environ Sci, 2010, 3: 174-189 CrossRef Google Scholar

[3] Gao J, Abruña HD. Key parameters governing the energy density of rechargeable Li/S batteries. J Phys Chem Lett, 2014, 5: 882-885 CrossRef PubMed Google Scholar

[4] Pang Q, Liang X, Kwok CY, et al. Advances in lithium–sulfur batteries based on multifunctional cathodes and electrolytes. Nat Energy, 2016, 1: 16132 CrossRef ADS Google Scholar

[5] Manthiram A, Fu Y, Chung SH, et al. Rechargeable lithium–sulfur batteries. Chem Rev, 2014, 114: 11751-11787 CrossRef PubMed Google Scholar

[6] Fang X, Peng H. A revolution in electrodes: recent progress in rechargeable lithium-sulfur batteries. Small, 2015, 11: 1488-1511 CrossRef PubMed Google Scholar

[7] Lai C, Gao XP, Zhang B, et al. Synthesis and electrochemical performance of sulfur/highly porous carbon composites. J Phys Chem C, 2009, 113: 4712-4716 CrossRef Google Scholar

[8] Xu T, Song J, Gordin ML, et al. Mesoporous carbon–carbon nanotube–sulfur composite microspheres for high-areal-capacity lithium–sulfur battery cathodes. ACS Appl Mater Interfaces, 2013, 5: 11355-11362 CrossRef PubMed Google Scholar

[9] Cheng XB, Huang JQ, Zhang Q, et al. Aligned carbon nanotube/sulfur composite cathodes with high sulfur content for lithium–sulfur batteries. Nano Energy, 2014, 4: 65-72 CrossRef Google Scholar

[10] Zhang Z, Jing HK, Liu S, et al. Encapsulating sulfur into a hybrid porous carbon/CNT substrate as a cathode for lithium–sulfur batteries. J Mater Chem A, 2015, 3: 6827-6834 CrossRef Google Scholar

[11] Babu G, Reddy Arava LM. Graphene-decorated graphite–sulfur composite as a high-tap-density electrode for Li–S batteries. RSC Adv, 2015, 5: 47621-47627 CrossRef Google Scholar

[12] Zhang Y, Li K, Huang J, et al. Preparation of monodispersed sulfur nanoparticles-partly reduced graphene oxide-polydopamine composite for superior performance lithium-sulfur battery. Carbon, 2017, 114: 8-14 CrossRef Google Scholar

[13] Zhang Y, Li K, Li H, et al. High sulfur loading lithium–sulfur batteries based on a upper current collector electrode with lithium-ion conductive polymers. J Mater Chem A, 2017, 5: 97-101 CrossRef Google Scholar

[14] Ji X, Lee KT, Nazar LF. A highly ordered nanostructured carbon–sulphur cathode for lithium–sulphur batteries. Nat Mater, 2009, 8: 500-506 CrossRef PubMed ADS Google Scholar

[15] Zhang B, Qin X, Li GR, et al. Enhancement of long stability of sulfur cathode by encapsulating sulfur into micropores of carbon spheres. Energy Environ Sci, 2010, 3: 1531-1537 CrossRef Google Scholar

[16] Li GC, Hu JJ, Li GR, et al. Sulfur/activated-conductive carbon black composites as cathode materials for lithium/sulfur battery. J Power Sources, 2013, 240: 598-605 CrossRef Google Scholar

[17] Li Z, Yuan L, Yi Z, et al. Insight into the electrode mechanism in lithium-sulfur batteries with ordered microporous carbon confined sulfur as the cathode. Adv Energy Mater, 2014, 4: 1301473 CrossRef Google Scholar

[18] Li GC, Li GR, Ye SH, et al. A polyaniline-coated sulfur/carbon composite with an enhanced high-rate capability as a cathode material for lithium/sulfur batteries. Adv Energy Mater, 2012, 2: 1238-1245 CrossRef Google Scholar

[19] Xie J, Yang J, Zhou X, et al. Preparation of three-dimensional hybrid nanostructure-encapsulated sulfur cathode for high-rate lithium sulfur batteries. J Power Sources, 2014, 253: 55-63 CrossRef ADS Google Scholar

[20] Li G, Sun J, Hou W, et al. Three-dimensional porous carbon composites containing high sulfur nanoparticle content for high-performance lithium–sulfur batteries. Nat Commun, 2016, 7: 10601 CrossRef PubMed ADS Google Scholar

[21] Zhang Z, Kong LL, Liu S, et al. A high-efficiency sulfur/carbon composite based on 3D graphene nanosheet@carbon nanotube matrix as cathode for lithium-sulfur battery. Adv Energy Mater, 2017, 7: 1602543 CrossRef Google Scholar

[22] Yang CP, Yin YX, Ye H, et al. Insight into the effect of boron doping on sulfur/carbon cathode in lithium–sulfur batteries. ACS Appl Mater Interfaces, 2014, 6: 8789-8795 CrossRef PubMed Google Scholar

[23] Qiu Y, Li W, Zhao W, et al. High-rate, ultralong cycle-life lithium/sulfur batteries enabled by nitrogen-doped graphene. Nano Lett, 2014, 14: 4821-4827 CrossRef PubMed ADS Google Scholar

[24] Zhou W, Wang C, Zhang Q, et al. Tailoring pore size of nitrogen-doped hollow carbon nanospheres for confining sulfur in lithium-sulfur batteries. Adv Energy Mater, 2015, 5: 1401752 CrossRef Google Scholar

[25] Zhou G, Paek E, Hwang GS, et al. Long-life Li/polysulphide batteries with high sulphur loading enabled by lightweight three-dimensional nitrogen/sulphur-codoped graphene sponge. Nat Commun, 2015, 6: 7760-7770 CrossRef PubMed ADS Google Scholar

[26] Wang L, Dong Z, Wang D, et al. Covalent bond glued sulfur nanosheet-based cathode integration for long-cycle-life Li–S batteries. Nano Lett, 2013, 13: 6244-6250 CrossRef PubMed ADS Google Scholar

[27] Zu C, Manthiram A. Hydroxylated graphene-sulfur nanocomposites for high-rate lithium-sulfur batteries. Adv Energy Mater, 2013, 3: 1008-1012 CrossRef Google Scholar

[28] Wang Z, Dong Y, Li H, et al. Enhancing lithium–sulphur battery performance by strongly binding the discharge products on amino-functionalized reduced graphene oxide. Nat Commun, 2014, 5: 5002-5009 CrossRef PubMed ADS Google Scholar

[29] Wei Seh Z, Li W, Cha JJ, et al. Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries. Nat Commun, 2013, 4: 1331-1336 CrossRef PubMed ADS Google Scholar

[30] Pang Q, Kundu D, Cuisinier M, et al. Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries. Nat Commun, 2014, 5: 4759-4766 CrossRef PubMed ADS Google Scholar

[31] Liang X, Kwok CY, Lodi-Marzano F, et al. Tuning transition metal oxide-sulfur interactions for long life lithium sulfur batteries: the “goldilocks” principle. Adv Energy Mater, 2016, 6: 1501636 CrossRef Google Scholar

[32] Tao X, Wang J, Liu C, et al. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design. Nat Commun, 2016, 7: 11203-11211 CrossRef PubMed ADS Google Scholar

[33] Fan Q, Liu W, Weng Z, et al. Ternary hybrid material for high-performance lithium–sulfur battery. J Am Chem Soc, 2015, 137: 12946-12953 CrossRef PubMed Google Scholar

[34] Yuan Z, Peng HJ, Hou TZ, et al. Powering lithium–sulfur battery performance by propelling polysulfide redox at sulfiphilic hosts. Nano Lett, 2016, 16: 519-527 CrossRef PubMed ADS Google Scholar

[35] Li X, Liang J, Lu Y, et al. Bi2S3 in-situ formed in molten S environment stabilized sulfur cathodes for high-performance lithium-sulfur batteries. J Power Sources, 2016, 329: 379-386 CrossRef ADS Google Scholar

[36] Lei T, Chen W, Huang J, et al. Multi-functional layered WS2 nanosheets for enhancing the performance of lithium-sulfur batteries. Adv Energy Mater, 2017, 7: 1601843 CrossRef Google Scholar

[37] Babu G, Masurkar N, Al Salem H, et al. Transition metal dichalcogenide atomic layers for lithium polysulfides electrocatalysis. J Am Chem Soc, 2017, 139: 171-178 CrossRef PubMed Google Scholar

[38] Cui Z, Zu C, Zhou W, et al. Mesoporous titanium nitride-enabled highly stable lithium-sulfur batteries. Adv Mater, 2016, 28: 6926-6931 CrossRef PubMed Google Scholar

[39] Deng DR, An TH, Li YJ, et al. Hollow porous titanium nitride tubes as a cathode electrode for extremely stable Li–S batteries. J Mater Chem A, 2016, 4: 16184-16190 CrossRef Google Scholar

[40] Hao Z, Yuan L, Chen C, et al. TiN as a simple and efficient polysulfide immobilizer for lithium–sulfur batteries. J Mater Chem A, 2016, 4: 17711-17717 CrossRef Google Scholar

[41] Sun Z, Zhang J, Yin L, et al. Conductive porous vanadium nitride/graphene composite as chemical anchor of polysulfides for lithium-sulfur batteries. Nat Commun, 2017, 8: 14627 CrossRef PubMed ADS Google Scholar

[42] Zhao X, Liu M, Chen Y, et al. Fabrication of layered Ti3C2 with an accordion-like structure as a potential cathode material for high performance lithium–sulfur batteries. J Mater Chem A, 2015, 3: 7870-7876 CrossRef Google Scholar

[43] Bao W, Su D, Zhang W, et al. 3D metal carbide@mesoporous carbon hybrid architecture as a new polysulfide reservoir for lithium-sulfur batteries. Adv Funct Mater, 2016, 26: 8746-8756 CrossRef Google Scholar

[44] Liang X, Rangom Y, Kwok CY, et al. Interwoven MXene nanosheet/carbon-nanotube composites as Li-S cathode hosts. Adv Mater, 2017, 29: 1603040 CrossRef PubMed Google Scholar

[45] Peng HJ, Zhang G, Chen X, et al. Enhanced electrochemical kinetics on conductive polar mediators for lithium-sulfur batteries. Angew Chem, 2016, 128: 13184-13189 CrossRef Google Scholar

[46] Liang X, Hart C, Pang Q, et al. A highly efficient polysulfide mediator for lithium–sulfur batteries. Nat Commun, 2015, 6: 5682-5689 CrossRef PubMed ADS Google Scholar

[47] Blöchl PE. Projector augmented-wave method. Phys Rev B, 1994, 50: 17953-17979 CrossRef ADS Google Scholar

[48] Kresse G, Joubert D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B, 1999, 59: 1758-1775 CrossRef ADS Google Scholar

[49] Perdew JP, Chevary JA, Vosko SH, et al. Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. Phys Rev B, 1992, 46: 6671-6687 CrossRef ADS Google Scholar

[50] Chinnasamy CN, Narayanasamy A, Ponpandian N, et al. Mixed spinel structure in nanocrystalline NiFe2O4. Phys Rev B, 2001, 63: 184108-184113 CrossRef ADS Google Scholar

[51] Carta D, Casula MF, Falqui A, et al. A structural and magnetic investigation of the inversion degree in ferrite nanocrystals MFe2O4 (M=Mn, Co, Ni). J Phys Chem C, 2009, 113: 8606-8615 CrossRef Google Scholar

[52] Rios E, Gautier JL, Poillerat G, et al. Mixed valency spinel oxides of transition metals and electrocatalysis: case of the MnxCo3−xO4 system. Electrochim Acta, 1998, 44: 1491-1497 CrossRef Google Scholar

[53] Ponpandian N, Balaya P, Narayanasamy A. Electrical conductivity and dielectric behaviour of nanocrystalline NiFe2O4 spinel. J Phys-Condens Matter, 2002, 14: 3221-3237 CrossRef ADS Google Scholar

[54] Zhao X, Fu Y, Wang J, et al. Ni-doped CoFe2O4 hollow nanospheres as efficient bi-functional catalysts. Electrochim Acta, 2016, 201: 172-178 CrossRef Google Scholar

[55] Zhang YZ, Zhang Z, Liu S, et al. Free-standing porous carbon nanofiber/carbon nanotube film as sulfur immobilizer with high areal capacity for lithium–sulfur battery. ACS Appl Mater Interfaces, 2018, 10: 8749-8757 CrossRef Google Scholar

[56] Cao Y, Li X, Zheng M, et al. Ultra-high rates and reversible capacity of Li-S battery with a nitrogen-doping conductive lewis base matrix. Electrochim Acta, 2016, 192: 467-474 CrossRef Google Scholar

  • Figure 1

    Preparation and characterization of the samples: (a) the schematic diagram of the structural formation and the preparation process, (b) XRD patterns of NiFe2O4 nanofibers and the S/NiFe2O4 composite, and (c) TG curve of the S/NiFe2O4 composite.

  • Figure 2

    XPS spectra: (a) Ni 2p, (b) Fe 2p and (c) O 1s of NiFe2O4 nanofibers; (d) O 1s and (e) S 2p of the S/NiFe2O4 composite; (f) S 2p of the S/CNT composite.

  • Figure 3

    Morphology features of the NiFe2O4 nanofibers and S/NiFe2O4 composite: TEM images of (a–c) NiFe2O4 nanofibers and (d) S/NiFe2O4 composite; (e) the TEM image recorded by the high angle annular dark field (HAADF) detector, and (f–i) the corresponding elemental mappings in the selected region of the S/NiFe2O4 composite.

  • Figure 4

    CVs of the (a) S/NiFe2O4 composite and (b) S/CNTcomposite with the potential range from 1.7 to 2.8 V (vs. Li/Li+) at the scan rate of 0.1 mV s−1; Comparison of the initial discharge/charge curve based on (c) gravimetric calculation and (d) volumetric calculation of the S/NiFe2O4 composite and S/CNT composite.

  • Figure 5

    The cycle stability in terms of (a) gravimetric capacity and (b) volumetric capacity at 0.1 C rate of S/NiFe2O4 and S/CNT composite.

  • Figure 6

    (a) The rate capability and (b) the initial discharge/charge curves of S/NiFe2O4 composite at various rates from 0.1 C to 2 C rate.

  • Figure 7

    Anchoring effect of polysulfide on spinel NiFe2O4 and CNTs: (a) UV-vis absorption spectra of 2 mmol L−1 Li2S8 solution (the inset shows the photos of sealed vials containing Li2S8 solutions before and after fully contacting with NiFe2O4 and CNTs); (b) the stable adsorption geometries of Li2S8 on both spinel NiFe2O4 and CNTs, and the atoms are marked in different colors: Li (pink), S (yellow), O (red), Ni (green), Fe (purple), C (grey); (c) the experimental quantities of Li2S8 adsorption; (d) the adsorption energy of Li2S8 on spinel NiFe2O4 and CNTs.

  • Figure 8

    EIS plots of the (a) S/NiFe2O4 and (b) S/CNT composites at full charged state at 0.1 C after different cycles. (c) EIS plots of the S/NiFe2O4 and S/CNT composites at the open circuit voltage and the used equivalent circuit to fit the experimental data.

  • Figure 9

    Cycle performance of S/MFe2O4 (M=Co, Mg, and Zn) composites at 0.1 C rate.

Copyright 2019 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有

京ICP备18024590号-1