Abstract
The severe shuttle effect problem of soluble polysulfides greatly hinders the development of long-life lithium-sulfur (Li-S) batteries, which can be improved by separator modification. This study develops a bilayer separator based on an effective surface and structure dual modification strategy. This bilayer separator (named as TCNFs/SPNFs) is constructed by the integration of a carbon-based nanofiber layer (surface modification layer) with a polymer-based nanofiber layer (structure modification layer) through a facile electrospinning process. The excellent electrolyte wettability of the nanofibers accelerates lithium-ion migration, while the good electronic conductivity of the carbon layer facilitates fast electron conduction. The TiO2 and SiO2 nanoparticles embedded in the separator provide abundant active sites for immobilizing the polysulfides. Owing to these synergistic effects, this multi-functional separator helps inhibit the shuttling problem and thus enhances the active sulfur utilization. The as-prepared battery with the TCNFs/SPNFs separator delivers significantly enhanced the electrochemical performances, producing a low capacity decay rate of 0.061% per cycle at 1 C over 1000 cycles and an admirable rate capacity of 886.7 mAh g−1 at 2 C. Even with a high sulfur loading of 4.8 mg cm−2, a remarkable areal capacity of 6.0 mAh cm−2 is attained. This work is believed to provide a promising strategy to develop novel separators for high performance Li-S batteries.
Similar content being viewed by others
References
Manthiram A, Fu Y, Chung S H, et al. Rechargeable lithium-sulfur batteries. Chem Rev, 2014, 114: 11751–11787
Fan M P, Chen Y M, Ke X, et al. In situ growth of NiS2 nanosheet array on Ni foil as cathode to improve the performance of lithium/sodium-sulfur batteries. Sci China Tech Sci, 2022, 65: 231–237
Wu K, Ning F, Yi J, et al. Host-guest supramolecular interaction behavior at the interface between anode and electrolyte for long life Zn anode. J Energy Chem, 2022, 69: 237–243
Wu K, Yi J, Liu X, et al. Regulating Zn deposition via an artificial solid-electrolyte interface with aligned dipoles for long life Zn anode. Nano-Micro Lett, 2021, 13: 79
Gao W, Wang Z, Peng C, et al. Accelerating the redox kinetics by catalytic activation of “dead sulfur” in lithium-sulfur batteries. J Mater Chem A, 2021, 9: 13442–13458
Lee S K, Lee Y J, Sun Y K. Nanostructured lithium sulfide materials for lithium-sulfur batteries. J Power Sources, 2016, 323: 174–188
Chen R, Zhao T, Wu F. From a historic review to horizons beyond: Lithium-sulphur batteries run on the wheels. Chem Commun, 2015, 51: 18–33
Liao K, Mao P, Li N, et al. Stabilization of polysulfides via lithium bonds for Li-S batteries. J Mater Chem A, 2016, 4: 5406–5409
Zhou K, Fan X J, Wei X F, et al. The strategies of advanced cathode composites for lithium-sulfur batteries. Sci China Tech Sci, 2017, 60: 175–185
Bai S, Zhu K, Wu S, et al. A long-life lithium-sulphur battery by integrating zinc-organic framework based separator. J Mater Chem A, 2016, 4: 16812–16817
Xu S N, Zhao T, Wang L L, et al. Endoplasmic-reticulum-like catalyst coating on separator to enhance polysulfides conversion for lithium-sulfur batteries. J Energy Chem, 2022, 67: 423–431
Jiang L, Hu Y, Cheng Z, et al. Excimer ultraviolet-irradiated carbon nanofibers with ZnO interlayer for strong binding to lithium polysulfides. Electrochim Acta, 2021, 375: 137993
Sung S H, Kim B H, Lee S T, et al. Increasing sulfur utilization in lithium-sulfur batteries by a Co-MOF-74@MWCNT interlayer. J Energy Chem, 2021, 60: 186–193
Jayaprakash N, Shen J, Moganty S S, et al. Porous hollow carbon@sulfur composites for high-power lithium-sulfur batteries. Angew Chem Int Ed, 2011, 50: 5904–5908
Li L, Hou L, Cheng J, et al. A flexible carbon/sulfur-cellulose core-shell structure for advanced lithium-sulfur batteries. Energy Storage Mater, 2018, 15: 388–395
Hong X, Wang R, Liu Y, et al. Recent advances in chemical adsorption and catalytic conversion materials for Li-S batteries. J Energy Chem, 2020, 42: 144–168
Tu S, Zhao X, Cheng M, et al. Uniform mesoporous MnO2 nanospheres as a surface chemical adsorption and physical confinement polysulfide mediator for lithium-sulfur batteries. ACS Appl Mater Interfaces, 2019, 11: 10624–10630
Liu D, Zhang C, Zhou G, et al. Catalytic effects in lithium-sulfur batteries: Promoted sulfur transformation and reduced shuttle effect. Adv Sci, 2018, 5: 1700270
Ye Z, Jiang Y, Li L, et al. A high-efficiency cose electrocatalyst with hierarchical porous polyhedron nanoarchitecture for accelerating polysulfides conversion in Li-S batteries. Adv Mater, 2020, 32: 2002168
Yin L C, Liang J, Zhou G M, et al. Understanding the interactions between lithium polysulfides and N-doped graphene using density functional theory calculations. Nano Energy, 2016, 25: 203–210
Yuan S, Bao J L, Wang L, et al. Graphene-supported nitrogen and boron rich carbon layer for improved performance of lithium-sulfur batteries due to enhanced chemisorption of lithium polysulfides. Adv Energy Mater, 2016, 6: 1501733
Cao B, Li D, Hou B, et al. Synthesis of double-shell SnO2@C hollow nanospheres as sulfur/sulfide cages for lithium-sulfur batteries. ACS Appl Mater Interfaces, 2016, 8: 27795–27802
Zhang R, Wu M, Fan X, et al. A Li-S battery with ultrahigh cycling stability and enhanced rate capability based on novel ZnO yolk-shell sulfur host. J Energy Chem, 2021, 55: 136–144
Cai W, Li G, Zhang K, et al. Conductive nanocrystalline niobium carbide as high-efficiency polysulfides tamer for lithium-sulfur batteries. Adv Funct Mater, 2018, 28: 1704865
Zhou F, Li Z, Luo X, et al. Low cost metal carbide nanocrystals as binding and electrocatalytic sites for high performance Li-S batteries. Nano Lett, 2018, 18: 1035–1043
Jiang G, Xu F, Yang S, et al. Mesoporous, conductive molybdenum nitride as efficient sulfur hosts for high-performance lithium-sulfur batteries. J Power Sources, 2018, 395: 77–84
Li Z, Ma Z, Wang Y, et al. LDHs derived nanoparticle-stacked metal nitride as interlayer for long-life lithium sulfur batteries. Sci Bull, 2018, 63: 169–175
Yuan Z, Peng H J, Hou T Z, et al. Powering lithium-sulfur battery performance by propelling polysulfide redox at sulfiphilic hosts. Nano Lett, 2016, 16: 519–527
Meng F C, Xu B, Long T, et al. ZnS nanolayer coated hollow carbon spheres with enhanced rate and cycling performance for Li-S batteries. Sci China Tech Sci, 2022, 65: 272–281
Wei Z, Ren Y, Sokolowski J, et al. Mechanistic understanding of the role separators playing in advanced lithium-sulfur batteries. InfoMat, 2020, 2: 483–508
Ponraj R, Kannan A G, Ahn J H, et al. Effective trapping of lithium polysulfides using a functionalized carbon nanotube-coated separator for lithium-sulfur cells with enhanced cycling stability. ACS Appl Mater Interfaces, 2017, 9: 38445–38454
Ma G, Huang F, Wen Z, et al. Enhanced performance of lithium sulfur batteries with conductive polymer modified separators. J Mater Chem A, 2016, 4: 16968–16974
Zhang Z, Lai Y, Zhang Z, et al. Al2O3-coated porous separator for enhanced electrochemical performance of lithium sulfur batteries. Electrochim Acta, 2014, 129: 55–61
Shao H, Wang W, Zhang H, et al. Nano-TiO2 decorated carbon coating on the separator to physically and chemically suppress the shuttle effect for lithium-sulfur battery. J Power Sources, 2018, 378: 537–545
Yuan W, Qiu Z, Wang C, et al. Design and interface optimization of a sandwich-structured cathode for lithium-sulfur batteries. Chem Eng J, 2020, 381: 122648
Xiang Y, Li J, Lei J, et al. Advanced separators for lithium-ion and lithium-sulfur batteries: A review of recent progress. ChemSusChem, 2016, 9: 3023–3039
Deng N, Kang W, Liu Y, et al. A review on separators for lithium sulfur battery: Progress and prospects. J Power Sources, 2016, 331: 132–155
Lei T, Chen W, Hu Y, et al. A nonflammable and thermotolerant separator suppresses polysulfide dissolution for safe and long-cycle lithium-sulfur batteries. Adv Energy Mater, 2018, 8: 1802441
Feng Y, Wang G, Kang W, et al. Taming polysulfides and facilitating lithium-ion migration: Novel electrospinning MOFs@PVDF-based composite separator with spiderweb-like structure for Li-S batteries. Electrochim Acta, 2021, 365: 137344
Zhang X, Yuan W, Yang Y, et al. Immobilizing polysulfide by in situ topochemical oxidation derivative TiC@carbon-included TiO2 core-shell sulfur hosts for advanced lithium-sulfur batteries. Small, 2020, 16: 2005998
Xue P, Guo C, Wang N, et al. Synergistic manipulation of Zn2+ ion flux and nucleation induction effect enabled by 3D hollow SiO2/TiO2/carbon fiber for long-lifespan and dendrite-free Zn-metal composite anodes. Adv Funct Mater, 2021, 31: 2106417
Huang J Q, Zhang B, Xu Z L, et al. Novel interlayer made from Fe3C/carbon nanofiber webs for high performance lithium-sulfur batteries. J Power Sources, 2015, 285: 43–50
Huo J, Xue Y, Wang X, et al. TiO2/carbon nanofibers doped with phosphorus as anodes for hybrid Li-ion capacitors. J Power Sources, 2020, 473: 228551
Li X, Chen S, Xia Z, et al. High performance of boehmite/polyacrylonitrile composite nanofiber membrane for polymer lithium-ion battery. RSC Adv, 2020, 10: 27492–27501
Dong X, Zheng X, Deng Y, et al. SiO2/N-doped graphene aerogel composite anode for lithium-ion batteries. J Mater Sci, 2020, 55: 13023–13035
Wang L, Yang G, Wang J, et al. Controllable design of MoS2 nanosheets grown on nitrogen-doped branched TiO2/C nanofibers: Toward enhanced sodium storage performance induced by pseudocapacitance behavior. Small, 2020, 16: 1904589
Li Y, Zhu J, Zhu P, et al. Glass fiber separator coated by porous carbon nanofiber derived from immiscible PAN/PMMA for high-performance lithium-sulfur batteries. J Membrane Sci, 2018, 552: 31–42
Zhu J, Yildirim E, Aly K, et al. Hierarchical multi-component nanofiber separators for lithium polysulfide capture in lithium-sulfur batteries: An experimental and molecular modeling study. J Mater Chem A, 2016, 4: 13572–13581
Zhang X, Yuan W, Yang Y, et al. Green and facile fabrication of porous titanium dioxide as efficient sulfur host for advanced lithium-sulfur batteries: An air oxidation strategy. J Colloid Interface Sci, 2021, 583: 157–165
Chen Y, Wang T, Tian H, et al. Advances in lithium-sulfur batteries: From academic research to commercial viability. Adv Mater, 2021, 33: 2003666
Ji L, Wang X, Jia Y, et al. Flexible electrocatalytic nanofiber membrane reactor for lithium/sulfur conversion chemistry. Adv Funct Mater, 2020, 30: 1910533
Hu Z, Su H, Tu S, et al. Efficient polysulfide trapping enabled by a polymer adsorbent in lithium-sulfur batteries. Electrochim Acta, 2020, 336: 135693
Wang D, Cao Q, Jing B, et al. A freestanding metallic tin-modified and nitrogen-doped carbon skeleton as interlayer for lithium-sulfur battery. Chem Eng J, 2020, 399: 125723
Zhou S, Liu J, Xie F, et al. A “boxes in fibers” strategy to construct a necklace-like conductive network for high-rate and high-loading lithium-sulfur batteries. J Mater Chem A, 2020, 8: 11327–11336
Jiang X, Zhang S, Zou B, et al. Electrospun CoSe@NC nanofiber membrane as an effective polysulfides adsorption-catalysis interlayer for Li-S batteries. Chem Eng J, 2022, 430: 131911
Zhao H, Deng N, Kang W, et al. The significant effect of octa(aminophenyl)silsesquioxane on the electrospun ion-selective and ultra-strong poly-m-phenyleneisophthalamide separator for enhanced electrochemical performance of lithium-sulfur battery. Chem Eng J, 2020, 381: 122715
Author information
Authors and Affiliations
Corresponding author
Additional information
This work was supported by the National Natural Science Foundation of China (Grant Nos. 51975218 and U22A20193), the Natural Science Foundation of Guangdong Province (Grant No. 2021A1515010642), Guangdong-Hong Kong Joint Innovation Project of Guangdong Province (Grant No. 2021A0505110002), Guangdong-Foshan Joint Foundation (Grant No. 2021B1515120031), the Innovation Group Project of Foshan (Grant No. 2120001010816), and the S&T Innovation Projects of Zhuhai City (Grant No. ZH01110405180034PWC).
Supporting Information
The supporting information is available online at tech.scichina.com and link.springer.com. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Xu, M., Zhang, X., Yuan, W. et al. Fabrication of electrospun bilayer separators for lithium-sulfur batteries: A surface and structure dual modification strategy. Sci. China Technol. Sci. 65, 3029–3038 (2022). https://doi.org/10.1007/s11431-022-2194-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11431-022-2194-2