High capacity micro-mesoporous carbon–sulfur nanocomposite cathodes with enhanced cycling stability prepared by a solvent-free procedure

The use of elemental sulfur as a cathode active material is challenging. Besides the complex electrochemical conversion mechanism there are negative side effects added to the system by application of solvent-based cathode preparation, such as chemical incompatibility caused by solvent contamination, sulfur evaporation and morphology change during drying as well as limited active material loading. Therefore we present a solvent-free, highly versatile pressing/thermal treatment method for the fast and reproducible production of mechanically stable and highly flexible freestanding carbon–sulfur composite cathode foils with tunable sulfur loading, high in-plane conductivity and enhanced cycling stability. Utilizing an optimized cathode composition consisting of sulfur, a porous carbon host material and a carbon nanotube conducting agent, a stable capacity >740 mA h g−1-S as well as high coulombic efficiency >96% was achieved over 160 cycles in our experiments at a moderate rate of C/10. Moreover, reversible cycling was possible up to a high rate of 1C due to the tuned carbon matrix properties as well as the highly conductive carbon nanotube percolation network. Thus not only a long-lasting electrical contact to insulating sulfur precipitates is provided but also the agglomeration of active material is restrained. To achieve even higher energy densities and improved corrosion resistance, the application of highly conductive freestanding cathode foils without a metallic current collector is a promising feature.

[1]  Bruno Scrosati,et al.  Rechargeable lithium sulfide electrode for a polymer tin/sulfur lithium-ion battery , 2011 .

[2]  Hee‐Tak Kim,et al.  Rechargeable Lithium Sulfur Battery II. Rate Capability and Cycle Characteristics , 2003 .

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

[4]  Jeffrey Read,et al.  A new direction for the performance improvement of rechargeable lithium/sulfur batteries , 2012 .

[5]  Sébastien Patoux,et al.  Lithium/sulfur cell discharge mechanism: an original approach for intermediate species identification. , 2012, Analytical chemistry.

[6]  Khalil Amine,et al.  Ultrasound Assisted Design of Sulfur/Carbon Cathodes with Partially Fluorinated Ether Electrolytes for Highly Efficient Li/S Batteries , 2013, Advanced materials.

[7]  L. Nazar,et al.  Advances in Li–S batteries , 2010 .

[8]  Kai Xie,et al.  Analysis of Polysulfide Dissolved in Electrolyte in Discharge-Charge Process of Li-S Battery , 2012 .

[9]  M. Oschatz,et al.  A cubic ordered, mesoporous carbide-derived carbon for gas and energy storage applications , 2010 .

[10]  L. Nazar,et al.  High “C” rate Li-S cathodes: sulfur imbibed bimodal porous carbons , 2011 .

[11]  Nansheng Xu,et al.  Sulfur-carbon nano-composite as cathode for rechargeable lithium battery based on gel electrolyte , 2002 .

[12]  L. Archer,et al.  Porous hollow carbon@sulfur composites for high-power lithium-sulfur batteries. , 2011, Angewandte Chemie.

[13]  Xiangming He,et al.  Expansion and shrinkage of the sulfur composite electrode in rechargeable lithium batteries , 2009 .

[14]  Emanuel Peled,et al.  Lithium Sulfur Battery Oxidation/Reduction Mechanisms of Polysulfides in THF Solutions , 1988 .

[15]  Zhen Zhou,et al.  Synthesis and Electrochemical Performance of Sulfur/Highly Porous Carbon Composites , 2009 .

[16]  Jou-Hyeon Ahn,et al.  Rechargeable lithium/sulfur battery with suitable mixed liquid electrolytes , 2007 .

[17]  Doron Aurbach,et al.  On the Surface Chemical Aspects of Very High Energy Density, Rechargeable Li–Sulfur Batteries , 2009 .

[18]  C. Liang,et al.  Hierarchically Structured Sulfur/Carbon Nanocomposite Material for High-Energy Lithium Battery , 2009 .

[19]  J. Tübke,et al.  High capacity vertical aligned carbon nanotube/sulfur composite cathodes for lithium-sulfur batteries. , 2012, Chemical communications.

[20]  Jung Tae Lee,et al.  High temperature stabilization of lithium–sulfur cells with carbon nanotube current collector , 2013 .

[21]  Jean-Marie Tarascon,et al.  Li-O2 and Li-S batteries with high energy storage. , 2011, Nature materials.

[22]  Shengdi Zhang.  Role of LiNO3 in rechargeable lithium/sulfur battery , 2012 .

[23]  K. Striebel,et al.  Electrochemical performance of lithium/sulfur cells with three different polymer electrolytes , 2000 .

[24]  B. Jung,et al.  Capacity Fading Mechanisms on Cycling a High-Capacity Secondary Sulfur Cathode , 2004 .

[25]  Jun Liu,et al.  Optimization of mesoporous carbon structures for lithium–sulfur battery applications , 2011 .

[26]  Petr Novák,et al.  Influence of different electrode compositions and binder materials on the performance of lithium–sulfur batteries , 2012 .

[27]  Doron Aurbach,et al.  Morphological and Structural Studies of Composite Sulfur Electrodes upon Cycling by HRTEM, AFM and Raman Spectroscopy , 2010 .

[28]  Yuriy V. Mikhaylik,et al.  Polysulfide Shuttle Study in the Li/S Battery System , 2004 .

[29]  Jason Xu,et al.  High Energy Rechargeable Li-S Cells for EV Application: Status, Remaining Problems and Solutions , 2010 .

[30]  L. Nazar,et al.  Spherical ordered mesoporous carbon nanoparticles with high porosity for lithium-sulfur batteries. , 2012, Angewandte Chemie.