Li-S Batteries with Li2S Cathodes and Si/C Anodes

Lithium-sulfur (Li-S) batteries promise improved capacities over lithium ion batteries. While currently mostly metallic lithium anodes are used, the use of silicon-anodes might offer better safety and durability. However, in a lithium-sulfur-Silicon (Li-S-Si) battery, lithium must be introduced either on the anode or on the cathode in form of Li2S. In this study, we have prepared Li2S cathodes in combination with Si anodes (i.e., Si/Li2S full-cells) to investigate both the processes during initial charging/activation of Li2S cathodes and the effect of Li2S cathode activation on the cycling performance of Si/Li2S full-cells. We observed that the initial activation requires a substantially higher charging potential than for the subsequent cycles. In situ XRD analysis of the cathode during the first cycle clearly indicates the gradual transformation of Li2S to polysulfides and finally to crystalline sulfur, i.e., even large Li2S particles (≈20 μm) can be charged completely. The result is further confirmed by ex-situ SEM/EDS analysis, which revealed the formation of large sheets of sulfur at the cathode/separator interface. Similar cycling performance of Si/Li2S full-cells is observed at both 0.1 C and 1 C rates, a clear advantage over Li/Li2S cells, which suffer from severe dendrite formation at 1 C in the case of high Li2S loadings. © The Author(s) 2015. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any medium, provided the original work is properly cited. [DOI: 10.1149/2.0681509jes] All rights reserved.

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

[2]  Shiro Seki,et al.  Solvate Ionic Liquid Electrolyte for Li–S Batteries , 2013 .

[3]  B. McCloskey,et al.  Nonaqueous Li-air batteries: a status report. , 2014, Chemical reviews.

[4]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[5]  K. M. Abraham,et al.  A Lithium/Dissolved Sulfur Battery with an Organic Electrolyte , 1979 .

[6]  Yong Liang,et al.  A High Capacity Nano ­ Si Composite Anode Material for Lithium Rechargeable Batteries , 1999 .

[7]  Yuhui Chen,et al.  The lithium-oxygen battery with ether-based electrolytes. , 2011, Angewandte Chemie.

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

[9]  Gregory V. Chase,et al.  Investigation of Fluorinated Amides for Solid–Electrolyte Interphase Stabilization in Li–O2 Batteries Using Amide-Based Electrolytes , 2013 .

[10]  Doron Aurbach,et al.  Exceptional electrochemical performance of Si-nanowires in 1,3-dioxolane solutions: a surface chemical investigation. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[11]  Bruno Scrosati,et al.  A high-performance polymer tin sulfur lithium ion battery. , 2010, Angewandte Chemie.

[12]  Doron Aurbach,et al.  Sulfur‐Impregnated Activated Carbon Fiber Cloth as a Binder‐Free Cathode for Rechargeable Li‐S Batteries , 2011, Advanced materials.

[13]  Arumugam Manthiram,et al.  Activated Li2S as a High-Performance Cathode for Rechargeable Lithium-Sulfur Batteries. , 2014, The journal of physical chemistry letters.

[14]  Linda F. Nazar,et al.  Towards a Stable Organic Electrolyte for the Lithium Oxygen Battery , 2015 .

[15]  K. Andreas Friedrich,et al.  In-situ X-ray diffraction studies of lithium-sulfur batteries , 2013 .

[16]  Stefan A Freunberger,et al.  The carbon electrode in nonaqueous Li-O2 cells. , 2013, Journal of the American Chemical Society.

[17]  Linda F. Nazar,et al.  Lithium-sulfur batteries , 2014 .

[18]  E. Cairns,et al.  Nanostructured Li₂S-C composites as cathode material for high-energy lithium/sulfur batteries. , 2012, Nano letters.

[19]  D. Aurbach,et al.  The Use of Redox Mediators for Enhancing Utilization of Li2S Cathodes for Advanced Li-S Battery Systems. , 2014, The journal of physical chemistry letters.

[20]  Xiulei Ji,et al.  Predicting capacity of hard carbon anodes in sodium-ion batteries using porosity measurements , 2014 .

[21]  Doron Aurbach,et al.  A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions , 2002 .

[22]  Stefano Meini,et al.  Rechargeability of Li-air cathodes pre-filled with discharge products using an ether-based electrolyte solution: implications for cycle-life of Li-air cells. , 2013, Physical chemistry chemical physics : PCCP.

[23]  Yi Cui,et al.  New nanostructured Li2S/silicon rechargeable battery with high specific energy. , 2010, Nano letters.

[24]  Michael F Toney,et al.  In Operando X-ray diffraction and transmission X-ray microscopy of lithium sulfur batteries. , 2012, Journal of the American Chemical Society.

[25]  Yi Cui,et al.  High-capacity micrometer-sized Li2S particles as cathode materials for advanced rechargeable lithium-ion batteries. , 2012, Journal of the American Chemical Society.

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

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

[28]  Doron Aurbach,et al.  Rechargeable lithiated silicon–sulfur (SLS) battery prototypes , 2012 .

[29]  Yi Cui,et al.  Prelithiated silicon nanowires as an anode for lithium ion batteries. , 2011, ACS nano.

[30]  Takashi Mori,et al.  Combining Accurate O2 and Li2O2 Assays to Separate Discharge and Charge Stability Limitations in Nonaqueous Li-O2 Batteries. , 2013, The journal of physical chemistry letters.

[31]  Kevin G. Gallagher,et al.  Quantifying the promise of lithium–air batteries for electric vehicles , 2014 .

[32]  Dipan Kundu,et al.  Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries , 2014, Nature Communications.

[33]  Jing Li,et al.  An In Situ X-Ray Diffraction Study of the Reaction of Li with Crystalline Si , 2007 .

[34]  H. Althues,et al.  Carbon‐Based Anodes for Lithium Sulfur Full Cells with High Cycle Stability , 2014 .

[35]  K. M. Abraham,et al.  A Polymer Electrolyte‐Based Rechargeable Lithium/Oxygen Battery , 1996 .

[36]  Mark N. Obrovac,et al.  Structural changes in silicon anodes during lithium insertion/extraction , 2004 .

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

[38]  Wei-Jun Zhang.  A review of the electrochemical performance of alloy anodes for lithium-ion batteries , 2011 .

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

[40]  Mark F. Mathias,et al.  Electrochemistry and the Future of the Automobile , 2010 .