High-performance lithium sulfur batteries enabled by a synergy between sulfur and carbon nanotubes

Abstract The urgent demand on high performance energy storage devices makes lithium sulfur batteries with a high energy density up to 2600 Wh kg−1 extremely attractive. However, the low capacity reversibility and poor rate capability still pose a significant hurdle on their real-world applications. Here, a freestanding thin-film composite containing sulfurized polyacrylonitrile with conductive backbone of carbon nanotubes has been fabricated by an electrospinning method followed by vulcanization, and employed as the binder-free cathode for lithium sulfur batteries without any aid of current collectors. A synergic effect from sulfur and carbon nanotubes, when co-spun together, has been discovered on promoting the electrochemical performance of the cathodes by simultaneously creating material porosity and conductive pathway. The optimized composite fibers made from a ternary precursor solution containing 20% carbon nanotubes present the best performance, delivering a high initial discharge capacity of 1610 mAh g−1 at 0.2C and outstanding cycle stability of 1106 mAh g−1 at 1C over 500 cycles. It is anticipated that the porous composite nanofibers and the multi-variant fabrication methodology reported here can be extended to more energy storage applications, particularly for flexible lithium sulfur batteries.

[1]  Jingying Xie,et al.  Lithium storage in conductive sulfur-containing polymers , 2004 .

[2]  M. Naebe,et al.  Sulfur-embedded porous carbon nanofiber composites for high stability lithium-sulfur batteries , 2018 .

[3]  R. Haddon,et al.  Electrochemical Lithiation of Covalently Bonded Sulfur in Vulcanized Polyisoprene , 2016 .

[4]  Keshi Wu,et al.  Facile fabrication of foldable electrospun polyacrylonitrile-based carbon nanofibers for flexible lithium-ion batteries , 2017 .

[5]  Tao Qian,et al.  Greatly Suppressed Shuttle Effect for Improved Lithium Sulfur Battery Performance through Short Chain Intermediates. , 2017, Nano letters.

[6]  M. Buchmeiser,et al.  Easily Accessible, Textile Fiber-Based Sulfurized Poly(acrylonitrile) as Li/S Cathode Material: Correlating Electrochemical Performance with Morphology and Structure , 2017 .

[7]  Lin Lu,et al.  Sulfur-graphene composite for rechargeable lithium batteries , 2011 .

[8]  J. Qian,et al.  Enhanced Performance of a Lithium-Sulfur Battery Using a Carbonate-Based Electrolyte. , 2016, Angewandte Chemie.

[9]  Zhian Zhang,et al.  Facile synthesis of graphene oxide @ mesoporous carbon hybrid nanocomposites for lithium sulfur battery , 2014 .

[10]  Naixin Xu,et al.  A novel conductive polymer-sulfur composite cathode material for rechargeable lithium batteries , 2002 .

[11]  Xiaogang Zhang,et al.  High performance lithium–sulfur batteries: advances and challenges , 2014 .

[12]  Bryan M. Wong,et al.  Solid state lithiation–delithiation of sulphur in sub-nano confinement: a new concept for designing lithium–sulphur batteries† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c5sc03419a , 2015, Chemical science.

[13]  Ling Huang,et al.  Graphitized porous carbon materials with high sulfur loading for lithium-sulfur batteries , 2017 .

[14]  Maximilian Fichtner,et al.  Single step transformation of sulphur to Li2S2/Li2S in Li-S batteries , 2015, Scientific Reports.

[15]  Junhe Yang,et al.  High Performance C/S Composite Cathodes with Conventional Carbonate-Based Electrolytes in Li-S Battery , 2014, Scientific Reports.

[16]  N. Zheng,et al.  Self-supporting sulfur cathodes enabled by two-dimensional carbon yolk-shell nanosheets for high-energy-density lithium-sulfur batteries , 2017, Nature Communications.

[17]  Shengbo Zhang.  Sulfurized Carbon: A Class of Cathode Materials for High Performance Lithium/Sulfur Batteries , 2013, Front. Energy Res..

[18]  H. Ahn,et al.  A ternary sulfur/polyaniline/carbon composite as cathode material for lithium sulfur batteries , 2013 .

[19]  Chunsheng Wang,et al.  Stabilizing high sulfur loading Li–S batteries by chemisorption of polysulfide on three-dimensional current collector , 2016 .

[20]  X. Lou,et al.  Pie-like electrode design for high-energy density lithium–sulfur batteries , 2015, Nature Communications.

[21]  M. Fukuhara,et al.  XPS studies on the chemical structure of the stabilized polyacrylonitrile fiber in the carbon fiber production process , 1986 .

[22]  Jiulin Wang,et al.  Sulfur‐Based Composite Cathode Materials for High‐Energy Rechargeable Lithium Batteries , 2015, Advanced materials.

[23]  Li Wang,et al.  Charge/discharge characteristics of sulfurized polyacrylonitrile composite with different sulfur content in carbonate based electrolyte for lithium batteries , 2012 .

[24]  Wenbin Zheng,et al.  Novel nanosized adsorbing sulfur composite cathode materials for the advanced secondary lithium batteries , 2006 .

[25]  Weidong Zhou,et al.  Amylopectin wrapped graphene oxide/sulfur for improved cyclability of lithium-sulfur battery. , 2013, ACS nano.

[26]  Guohua Chen,et al.  Novel hierarchically porous carbon materials obtained from natural biopolymer as host matrixes for lithium-sulfur battery applications. , 2014, ACS applied materials & interfaces.

[27]  L. Nazar,et al.  A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries. , 2009, Nature materials.

[28]  Fengyuan Yang,et al.  The synthesis of polyacrylonitrile/carbon nanotube microspheres by aqueous deposition polymerization under ultrasonication , 2010 .

[29]  Yuliang Cao,et al.  Sulfur/carbon nanocomposite-filled polyacrylonitrile nanofibers as a long life and high capacity cathode for lithium–sulfur batteries , 2015 .

[30]  Yi Cui,et al.  Facile synthesis of Li2S–polypyrrole composite structures for high-performance Li2S cathodes , 2014 .

[31]  Pu Chen,et al.  Effect of Graphene on Sulfur/Polyacrylonitrile Nanocomposite Cathode in High Performance Lithium/Sulfur Batteries , 2013 .

[32]  Jiulin Wang,et al.  A novel pyrolyzed polyacrylonitrile-sulfur@MWCNT composite cathode material for high-rate rechargeable lithium/sulfur batteries , 2011 .

[33]  Shengbo Zhang.  Understanding of Sulfurized Polyacrylonitrile for Superior Performance Lithium/Sulfur Battery , 2014 .

[34]  Hong‐Jie Peng,et al.  Unstacked double-layer templated graphene for high-rate lithium–sulphur batteries , 2014, Nature Communications.

[35]  Nansheng Xu,et al.  Sulfur Composite Cathode Materials for Rechargeable Lithium Batteries , 2003 .

[36]  High performance freestanding composite cathode for lithium-sulfur batteries , 2016 .

[37]  L. Nazar,et al.  Long-Life and High-Areal-Capacity Li-S Batteries Enabled by a Light-Weight Polar Host with Intrinsic Polysulfide Adsorption. , 2016, ACS nano.

[38]  Donghai Wang,et al.  Porous spherical polyacrylonitrile-carbon nanocomposite with high loading of sulfur for lithium–sulfur batteries , 2016 .

[39]  R. Stepanyan,et al.  Nanofiber diameter in electrospinning of polymer solutions: Model and experiment , 2016 .

[40]  Pu Chen,et al.  Binding mechanism of sulfur and dehydrogenated polyacrylonitrile in sulfur/polymer composite cathode , 2013 .

[41]  Xueping Gao,et al.  Microporous Carbon Polyhedrons Encapsulated Polyacrylonitrile Nanofibers as Sulfur Immobilizer for Lithium-Sulfur Battery. , 2017, ACS applied materials & interfaces.

[42]  Chunsheng Wang,et al.  Sulfur-impregnated disordered carbon nanotubes cathode for lithium-sulfur batteries. , 2011, Nano letters.

[43]  P. Chen,et al.  Cyclability of sulfur/dehydrogenated polyacrylonitrile composite cathode in lithium–sulfur batteries , 2013, Journal of Solid State Electrochemistry.

[44]  Yingchao Yu,et al.  Yolk-shell structure of polyaniline-coated sulfur for lithium-sulfur batteries. , 2013, Journal of the American Chemical Society.

[45]  Guoqiang Ma,et al.  A conductive selenized polyacrylonitrile cathode material for re-chargeable lithium batteries with long cycle life , 2015 .

[46]  Junhua Song,et al.  One-step synthesis of carbon nanosheet-decorated carbon nanofibers as a 3D interconnected porous carbon scaffold for lithium–sulfur batteries , 2017 .

[47]  P. Shen,et al.  Sulfur-infiltrated three-dimensional graphene-like material with hierarchical pores for highly stable lithium–sulfur batteries , 2014 .

[48]  W. Lu,et al.  In situ wrapping of the cathode material in lithium-sulfur batteries , 2017, Nature Communications.

[49]  Xiao Liang,et al.  A highly efficient polysulfide mediator for lithium–sulfur batteries , 2015, Nature Communications.

[50]  Christopher J. Ellison,et al.  Trapping lithium polysulfides of a Li–S battery by forming lithium bonds in a polymer matrix , 2015 .

[51]  Kenville E. Hendrickson,et al.  Metal-Sulfur Battery Cathodes Based on PAN-Sulfur Composites. , 2015, Journal of the American Chemical Society.

[52]  Ya‐Xia Yin,et al.  Electrochemical (de)lithiation of 1D sulfur chains in Li-S batteries: a model system study. , 2015, Journal of the American Chemical Society.

[53]  Jiulin Wang,et al.  Polyacrylonitrile/graphene composite as a precursor to a sulfur-based cathode material for high-rate rechargeable Li–S batteries , 2012 .

[54]  R. Carter,et al.  Sulfur Vapor-Infiltrated 3D Carbon Nanotube Foam for Binder-Free High Areal Capacity Lithium-Sulfur Battery Composite Cathodes. , 2017, ACS nano.

[55]  Pu Chen,et al.  Ternary sulfur/polyacrylonitrile/Mg0.6Ni0.4O composite cathodes for high performance lithium/sulfur batteries , 2012 .

[56]  Yi Cui,et al.  Designing high-energy lithium-sulfur batteries. , 2016, Chemical Society reviews.

[57]  M. Naebe,et al.  A review of recent developments in rechargeable lithium-sulfur batteries. , 2016, Nanoscale.