Nanomaterials: Science and applications in the lithium–sulfur battery

Summary Reliable and cost-effective technologies for electrical energy storage are in great demand in sectors of the global economy ranging from portable devices, transportation, and sustainable production of electricity from intermittent sources. Among the various electrochemical energy storage options under consideration, rechargeable lithium–sulfur (Li–S) batteries remain the most promising platform for reversibly storing large amounts of electrical energy at moderate cost set by the inherent cell chemistry. The success of Li–S storage technology in living up to this promise calls for solutions to fundamental problems associated with the inherently low electrical conductivity of sulfur and sulfides, and the complex solution chemistry of lithiated sulfur compounds in commonly used electrolytes. These problems appear well posed for innovative solutions using nanomaterials and for fundamental answers guided by the tools of nanotechnology. Beginning with a review of the current understanding of Li–S battery chemistry and operation, this review discusses how advances in nano-characterization and theoretical studies of the Li–S system are helping advance the understanding of the Li–S battery. Factors that prevent Li–S cells from realizing the theoretical capacity set by their chemistry are discussed both in terms of the impressive advances in cell design enabled by nanomaterials and recent progress aimed at nanoengineering the cathode and other cell components. Perspectives and directions for future development of the Li–S storage platform are discussed based on accumulated knowledge from previous efforts in the field as well as from the accumulated experience of the writers of this review.

[1]  B. Meyer SOLID ALLOTROPES OF SULFUR , 1964 .

[2]  Xinping Qiu,et al.  New insight into the discharge process of sulfur cathode by electrochemical impedance spectroscopy , 2009 .

[3]  Yang Liu,et al.  A highly ordered meso@microporous carbon-supported sulfur@smaller sulfur core-shell structured cathode for Li-S batteries. , 2014, ACS nano.

[4]  Feng Li,et al.  Carbon–sulfur composites for Li–S batteries: status and prospects , 2013 .

[5]  A. Manthiram,et al.  Enhanced Cyclability of Lithium–Sulfur Batteries by a Polymer Acid-Doped Polypyrrole Mixed Ionic–Electronic Conductor , 2012 .

[6]  Xiangyang Zhou,et al.  Functionalized N-Doped Porous Carbon Nanofiber Webs for a Lithium–Sulfur Battery with High Capacity and Rate Performance , 2014 .

[7]  Ziqi Wang,et al.  A Metal–Organic Framework with Open Metal Sites for Enhanced Confinement of Sulfur and Lithium–Sulfur Battery of Long Cycling Life , 2013 .

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

[9]  Peter G. Bruce,et al.  Energy storage beyond the horizon: Rechargeable lithium batteries , 2008 .

[10]  Yan Zhao,et al.  One-step synthesis of branched sulfur/polypyrrole nanocomposite cathode for lithium rechargeable batteries , 2012 .

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

[12]  R. Dominko,et al.  Application of in operando UV/Vis spectroscopy in lithium-sulfur batteries. , 2014, ChemSusChem.

[13]  Jitong Wang,et al.  A high-rate lithium–sulfur battery assisted by nitrogen-enriched mesoporous carbons decorated with ultrafine La2O3 nanoparticles , 2013 .

[14]  Arumugam Manthiram,et al.  Rechargeable lithium-sulfur batteries. , 2014, Chemical reviews.

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

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

[17]  L. Archer,et al.  Lithium-sulfur battery cathode enabled by lithium-nitrile interaction. , 2013, Journal of the American Chemical Society.

[18]  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.

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

[20]  Zaiping Guo,et al.  Investigation of discharge reaction mechanism of lithium|liquid electrolyte|sulfur battery , 2009 .

[21]  L. Nazar,et al.  Unique behaviour of nonsolvents for polysulphides in lithium–sulphur batteries , 2014 .

[22]  Yi Cui,et al.  Improved lithium–sulfur batteries with a conductive coating on the separator to prevent the accumulation of inactive S-related species at the cathode–separator interface , 2014 .

[23]  Wook Ki Jung,et al.  Encapsulated Monoclinic Sulfur for Stable Cycling of Li–S Rechargeable Batteries , 2013, Advanced materials.

[24]  Guangyuan Zheng,et al.  Amphiphilic surface modification of hollow carbon nanofibers for improved cycle life of lithium sulfur batteries. , 2013, Nano letters.

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

[26]  Shichao Zhang,et al.  Preparation and enhanced electrochemical properties of nano-sulfur/poly(pyrrole-co-aniline) cathode material for lithium/sulfur batteries , 2010 .

[27]  A. Manthiram,et al.  Challenges and prospects of lithium-sulfur batteries. , 2013, Accounts of chemical research.

[28]  Shi-Gang Sun,et al.  A composite material of uniformly dispersed sulfur on reduced graphene oxide: Aqueous one-pot synthesis, characterization and excellent performance as the cathode in rechargeable lithium-sulfur batteries , 2012, Nano Research.

[29]  Rajeev S. Assary,et al.  Toward a Molecular Understanding of Energetics in Li–S Batteries Using Nonaqueous Electrolytes: A High-Level Quantum Chemical Study , 2014 .

[30]  Zhian Zhang,et al.  Confine sulfur in mesoporous metal–organic framework @ reduced graphene oxide for lithium sulfur battery , 2014 .

[31]  Xiao Xing Liang,et al.  Improved cycling performances of lithium sulfur batteries with LiNO 3-modified electrolyte , 2011 .

[32]  Yu-Guo Guo,et al.  Tuning the porous structure of carbon hosts for loading sulfur toward long lifespan cathode materials for Li–S batteries , 2013 .

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

[34]  Yi Cui,et al.  Strong sulfur binding with conducting Magnéli-phase Ti(n)O2(n-1) nanomaterials for improving lithium-sulfur batteries. , 2014, Nano letters.

[35]  Hong‐Jie Peng,et al.  Ionic shield for polysulfides towards highly-stable lithium–sulfur batteries , 2014 .

[36]  Arumugam Manthiram,et al.  Lithium–sulphur batteries with a microporous carbon paper as a bifunctional interlayer , 2012, Nature Communications.

[37]  A. Manthiram,et al.  Lithium–sulfur batteries with superior cycle stability by employing porous current collectors , 2013 .

[38]  Leon L. Shaw,et al.  Recent advances in lithium–sulfur batteries , 2014 .

[39]  Xin-bo Zhang,et al.  Facile and effective synthesis of reduced graphene oxide encapsulated sulfur via oil/water system for high performance lithium sulfur cells , 2012 .

[40]  Li-Jun Wan,et al.  Lithium-sulfur batteries: electrochemistry, materials, and prospects. , 2013, Angewandte Chemie.

[41]  Jou-Hyeon Ahn,et al.  Effects of carbon coating on the electrochemical properties of sulfur cathode for lithium/sulfur cell , 2008 .

[42]  Weikun Wang,et al.  Pig bone derived hierarchical porous carbon and its enhanced cycling performance of lithium–sulfur batteries , 2011 .

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

[44]  J. Cabana,et al.  X-ray Absorption Spectra of Dissolved Polysulfides in Lithium-Sulfur Batteries from First-Principles. , 2014, The journal of physical chemistry letters.

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

[46]  Kyoung-Hee Shin,et al.  Synthesis and electrochemical properties of a sulfur-multi walled carbon nanotubes composite as a cathode material for lithium sulfur batteries , 2012 .

[47]  L. Stievano,et al.  X-ray absorption near-edge structure and nuclear magnetic resonance study of the lithium-sulfur battery and its components. , 2014, Chemphyschem : a European journal of chemical physics and physical chemistry.

[48]  Céline Barchasz,et al.  New insight into the working mechanism of lithium-sulfur batteries: in situ and operando X-ray diffraction characterization. , 2013, Chemical communications.

[49]  Guangyuan Zheng,et al.  Nanostructured sulfur cathodes. , 2013, Chemical Society reviews.

[50]  Chuan Yi Tang,et al.  A 2.|E|-Bit Distributed Algorithm for the Directed Euler Trail Problem , 1993, Inf. Process. Lett..

[51]  Z. Wen,et al.  A composite of sulfur and polypyrrole–multi walled carbon combinatorial nanotube as cathode for Li/S battery , 2012 .

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

[53]  Shizhao Xiong,et al.  Properties of surface film on lithium anode with LiNO3 as lithium salt in electrolyte solution for lithium–sulfur batteries , 2012 .

[54]  Guohua Chen,et al.  The superior cycle and rate performance of a novel sulfur cathode by immobilizing sulfur into porous N-doped carbon microspheres. , 2014, Chemical communications.

[55]  Huichao Chen,et al.  High efficiency immobilization of sulfur on nitrogen-enriched mesoporous carbons for Li-S batteries. , 2013, ACS applied materials & interfaces.

[56]  Jun Liu,et al.  A Soft Approach to Encapsulate Sulfur: Polyaniline Nanotubes for Lithium‐Sulfur Batteries with Long Cycle Life , 2012, Advanced materials.

[57]  Ilias Belharouak,et al.  Role of Polysulfides in Self‐Healing Lithium–Sulfur Batteries , 2013 .

[58]  Jie Gao,et al.  Key Parameters Governing the Energy Density of Rechargeable Li/S Batteries. , 2014, The journal of physical chemistry letters.

[59]  Lei Wang,et al.  Porous carbon nanofiber–sulfur composite electrodes for lithium/sulfur cells , 2011 .

[60]  Qiang Sun,et al.  Synthesis of superior carbon nanofibers with large aspect ratio and tunable porosity for electrochemical energy storage , 2013 .

[61]  Yuriy V. Mikhaylik,et al.  Li/S fundamental chemistry and application to high-performance rechargeable batteries , 2004 .

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

[63]  Jing Liang,et al.  A quantum-chemical study on the discharge reaction mechanism of lithium-sulfur batteries , 2013 .

[64]  Lin Gu,et al.  Smaller sulfur molecules promise better lithium-sulfur batteries. , 2012, Journal of the American Chemical Society.

[65]  Guangyuan Zheng,et al.  Hollow carbon nanofiber-encapsulated sulfur cathodes for high specific capacity rechargeable lithium batteries. , 2011, Nano letters.

[66]  M. Buchmeiser,et al.  Structure-Related Electrochemistry of Sulfur-Poly(acrylonitrile) Composite Cathode Materials for Rechargeable Lithium Batteries , 2011 .

[67]  X. Tao,et al.  Highly mesoporous carbon foams synthesized by a facile, cost-effective and template-free Pechini method for advanced lithium–sulfur batteries , 2013 .

[68]  X. Lou,et al.  Confining sulfur in double-shelled hollow carbon spheres for lithium-sulfur batteries. , 2012, Angewandte Chemie.

[69]  K. W. Kim,et al.  Electrochemical properties of sulfur electrode containing nano Al2O3 for lithium/sulfur cell , 2007 .

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

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

[72]  Jean-Marie Tarascon,et al.  Li–S batteries: simple approaches for superior performance , 2013 .

[73]  S. Pantelides,et al.  Formation of Large Polysulfide Complexes during the Lithium-Sulfur Battery Discharge , 2014 .

[74]  Shizhao Xiong,et al.  Oxidation process of polysulfides in charge process for lithium–sulfur batteries , 2012, Ionics.

[75]  H. Dai,et al.  Graphene-wrapped sulfur particles as a rechargeable lithium-sulfur battery cathode material with high capacity and cycling stability. , 2011, Nano letters.

[76]  L. Archer,et al.  In situ synthesis of lithium sulfide–carbon composites as cathode materials for rechargeable lithium batteries , 2013 .

[77]  Arumugam Manthiram,et al.  Orthorhombic Bipyramidal Sulfur Coated with Polypyrrole Nanolayers As a Cathode Material for Lithium–Sulfur Batteries , 2012 .

[78]  L. Archer,et al.  Tethered Molecular Sorbents: Enabling Metal‐Sulfur Battery Cathodes , 2014 .

[79]  Zhichuan J. Xu,et al.  Encapsulating MWNTs into Hollow Porous Carbon Nanotubes: A Tube‐in‐Tube Carbon Nanostructure for High‐Performance Lithium‐Sulfur Batteries , 2014, Advanced materials.

[80]  L. Nazar,et al.  New approaches for high energy density lithium-sulfur battery cathodes. , 2013, Accounts of chemical research.

[81]  Li Li,et al.  Sulfur/Polythiophene with a Core/Shell Structure: Synthesis and Electrochemical Properties of the Cathode for Rechargeable Lithium Batteries , 2011 .

[82]  Yi Cui,et al.  Improving the performance of lithium-sulfur batteries by conductive polymer coating. , 2011, ACS nano.

[83]  L. Nazar,et al.  Graphene-enveloped sulfur in a one pot reaction: a cathode with good coulombic efficiency and high practical sulfur content. , 2012, Chemical communications.

[84]  Jin-Song Hu,et al.  Nanostructured Materials for Electrochemical Energy Conversion and Storage Devices , 2008 .

[85]  Guangyuan Zheng,et al.  A membrane-free lithium/polysulfide semi-liquid battery for large-scale energy storage , 2013 .

[86]  P. T. Cunningham,et al.  Phase Equilibria in Lithium‐Chalcogen Systems II . Lithium‐Sulfur , 1971 .

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

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

[89]  K. Andreas Friedrich,et al.  Experimental and Theoretical Analysis of Products and Reaction Intermediates of Lithium−Sulfur Batteries , 2014 .

[90]  Yaqin Huang,et al.  Structural change of the porous sulfur cathode using gelatin as a binder during discharge and charge , 2009 .

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

[92]  Feixiang Wu,et al.  Nanoporous Li2S and MWCNT-linked Li2S powder cathodes for lithium-sulfur and lithium-ion battery chemistries , 2014 .

[93]  B. Dunn,et al.  Electrical Energy Storage for the Grid: A Battery of Choices , 2011, Science.

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

[95]  Gérard Férey,et al.  Cathode composites for Li-S batteries via the use of oxygenated porous architectures. , 2011, Journal of the American Chemical Society.

[96]  Z. Wen,et al.  A nano-structured and highly ordered polypyrrole-sulfur cathode for lithiumsulfur batteries , 2011 .

[97]  Shengbo Zhang,et al.  Liquid electrolyte lithium/sulfur battery: Fundamental chemistry, problems, and solutions , 2013 .

[98]  Linda F. Nazar,et al.  Sulfur Speciation in Li–S Batteries Determined by Operando X-ray Absorption Spectroscopy , 2013 .

[99]  Linda F. Nazar,et al.  Understanding the Nature of Absorption/Adsorption in Nanoporous Polysulfide Sorbents for the Li–S Battery , 2012 .

[100]  Shizhao Xiong,et al.  On the role of polysulfides for a stable solid electrolyte interphase on the lithium anode cycled in lithium–sulfur batteries , 2013 .

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

[102]  Jun Chen,et al.  Sulphur-polypyrrole composite positive electrode materials for rechargeable lithium batteries , 2006 .

[103]  Yang‐Kook Sun,et al.  Nickel-Layer Protected, Carbon-Coated Sulfur Electrode for Lithium Battery , 2012 .

[104]  Xueping Gao,et al.  Enhancement of long stability of sulfur cathode by encapsulating sulfur into micropores of carbon spheres , 2010 .

[105]  Kenville E. Hendrickson,et al.  Model Membrane‐Free Li–S Batteries for Enhanced Performance and Cycle Life , 2015, Advanced science.

[106]  Yang-Kook Sun,et al.  Challenges facing lithium batteries and electrical double-layer capacitors. , 2012, Angewandte Chemie.

[107]  Hee‐Tak Kim,et al.  Rechargeable Lithium Sulfur Battery I. Structural Change of Sulfur Cathode During Discharge and Charge , 2003 .

[108]  P. Bruce,et al.  Nanostructured materials for advanced energy conversion and storage devices , 2005, Nature materials.

[109]  Kyu-Tae Lee,et al.  Inhibiting the shuttle effect in lithium–sulfur batteries using a layer-by-layer assembled ion-permselective separator , 2014 .

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

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

[112]  C. Liang,et al.  Lithium superionic sulfide cathode for all-solid lithium-sulfur batteries. , 2013, ACS nano.

[113]  Xiulei Ji,et al.  Stabilizing lithium-sulphur cathodes using polysulphide reservoirs. , 2011, Nature Communications.

[114]  Jianming Zheng,et al.  Manipulating surface reactions in lithium–sulphur batteries using hybrid anode structures , 2014, Nature Communications.

[115]  Kai Xie,et al.  Characterization of the solid electrolyte interphase on lithium anode for preventing the shuttle mechanism in lithium–sulfur batteries , 2014 .

[116]  Zhijun Ling,et al.  Polymer lithium cells with sulfur composites as cathode materials , 2003 .

[117]  Qian Zhang,et al.  A hierarchical architecture S/MWCNT nanomicrosphere with large pores for lithium sulfur batteries. , 2012, Physical chemistry chemical physics : PCCP.

[118]  Jie Gao,et al.  Mechanistic insights into operational lithium–sulfur batteries by in situ X-ray diffraction and absorption spectroscopy , 2014 .

[119]  Guangyuan Zheng,et al.  High-performance hollow sulfur nanostructured battery cathode through a scalable, room temperature, one-step, bottom-up approach , 2013, Proceedings of the National Academy of Sciences.

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

[121]  Xinping Qiu,et al.  Improvement of cycle property of sulfur-coated multi-walled carbon nanotubes composite cathode for lithium/sulfur batteries , 2009 .

[122]  Xiao-Guang Sun,et al.  Lithium-sulfur batteries based on nitrogen-doped carbon and an ionic-liquid electrolyte. , 2012, ChemSusChem.

[123]  Rong Xu,et al.  Embedding sulfur in MOF-derived microporous carbon polyhedrons for lithium-sulfur batteries. , 2013, Chemistry.

[124]  Jaephil Cho,et al.  Roles of nanosize in lithium reactive nanomaterials for lithium ion batteries , 2011 .

[125]  Robert Dominko,et al.  Li-S battery analyzed by UV/Vis in operando mode. , 2013, ChemSusChem.

[126]  R. Li,et al.  Tailoring interactions of carbon and sulfur in Li-S battery cathodes: significant effects of carbon- heteroatom bonds† , 2014 .

[127]  X. Lou,et al.  Enhancing lithium–sulphur battery performance by strongly binding the discharge products on amino-functionalized reduced graphene oxide , 2014, Nature Communications.

[128]  Bruno Scrosati,et al.  Recent progress and remaining challenges in sulfur-based lithium secondary batteries--a review. , 2013, Chemical communications.

[129]  Jinghua Guo,et al.  Electronic structure and chemical bonding of a graphene oxide-sulfur nanocomposite for use in superior performance lithium-sulfur cells. , 2012, Physical chemistry chemical physics : PCCP.

[130]  Jung Ho Yu,et al.  Two-dimensional layered transition metal disulphides for effective encapsulation of high-capacity lithium sulphide cathodes , 2014, Nature Communications.

[131]  Arumugam Manthiram,et al.  Highly reversible Li/dissolved polysulfide batteries with binder-free carbon nanofiber electrodes , 2013 .

[132]  Jou-Hyeon Ahn,et al.  Discharge process of Li/PVdF/S cells at room temperature , 2006 .

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

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

[135]  Guoqiang Ma,et al.  A lithium anode protection guided highly-stable lithium-sulfur battery. , 2014, Chemical communications.

[136]  Chunsheng Wang,et al.  Copper‐Stabilized Sulfur‐Microporous Carbon Cathodes for Li–S Batteries , 2014 .

[137]  Ji‐Guang Zhang,et al.  Lewis acid-base interactions between polysulfides and metal organic framework in lithium sulfur batteries. , 2014, Nano letters.

[138]  Ming Jia,et al.  Nickel foam as interlayer to improve the performance of lithium–sulfur battery , 2014, Journal of Solid State Electrochemistry.

[139]  Bruno Scrosati,et al.  Moving to a Solid‐State Configuration: A Valid Approach to Making Lithium‐Sulfur Batteries Viable for Practical Applications , 2010, Advanced materials.

[140]  Jun Chen,et al.  Sulfur–mesoporous carbon composites in conjunction with a novel ionic liquid electrolyte for lithium rechargeable batteries , 2008 .

[141]  Yusheng Yang,et al.  A high sulfur content composite with core–shell structure as cathode material for Li–S batteries , 2013 .

[142]  Haoshen Zhou,et al.  Nanomaterials for lithium ion batteries , 2006 .