A robust sulfur host with dual lithium polysulfide immobilization mechanism for long cycle life and high capacity Li-S batteries

Abstract Beyond the physical lithium polysulfide (Li2Sx) entrapment of various 3D porous sulfur hosts, the importance of chemical interactions between sulfur host and Li2Sx on performance of Li-S batteries has recently been highlighted. However, most of these studies focus mainly on one type of chemical interaction and effective suppression of Li2Sx migration is still lacking. Here, we report a uniquely designed sulfur host that can immobilize Li2Sx through a dual chemisorption mechanism. The new sulfur host is consisted of an MXene matrix and polydopamine (PDA) overcoat, where Mxene forms a strong Ti–S bonding by the Lewis acid-base mechanism while PDA withholds Li2Sx through the polar-polar interaction. Benefited from the double chemisorption, the new cathode with a high sulfur loading of 5 mg cm−2 has been demonstrated with an initial capacity of 1001 mA h g−1 at a capacity retention of 65% over 1000 cycles at 0.2 C. Overall, this study not only presents a unique chemical mechanism to entrap Li2Sx, but also provides a new way to rationally design a practical sulfur cathode for high-performance Li-S batteries.

[1]  Jianming Zheng,et al.  High Energy Density Lithium–Sulfur Batteries: Challenges of Thick Sulfur Cathodes , 2015 .

[2]  Chaoyi Yan,et al.  Multi‐Functional Layered WS2 Nanosheets for Enhancing the Performance of Lithium–Sulfur Batteries , 2017 .

[3]  Xiao Liang,et al.  Sulfur cathodes based on conductive MXene nanosheets for high-performance lithium-sulfur batteries. , 2015, Angewandte Chemie.

[4]  M. Zheng,et al.  Conductive Lewis Base Matrix to Recover the Missing Link of Li2S8 during the Sulfur Redox Cycle in Li–S Battery , 2015 .

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

[6]  Tingzheng Hou,et al.  Design Principles for Heteroatom-Doped Nanocarbon to Achieve Strong Anchoring of Polysulfides for Lithium-Sulfur Batteries. , 2016, Small.

[7]  Hyun‐Wook Lee,et al.  In Situ Observation and Electrochemical Study of Encapsulated Sulfur Nanoparticles by MoS2 Flakes. , 2017, Journal of the American Chemical Society.

[8]  Jing Xu,et al.  Confined Sulfur in 3 D MXene/Reduced Graphene Oxide Hybrid Nanosheets for Lithium-Sulfur Battery. , 2017, Chemistry.

[9]  Linda F. Nazar,et al.  Advances in lithium–sulfur batteries based on multifunctional cathodes and electrolytes , 2016, Nature Energy.

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

[11]  X. Tao,et al.  Facilitation of sulfur evolution reaction by pyridinic nitrogen doped carbon nanoflakes for highly-stable lithium-sulfur batteries , 2018 .

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

[13]  Hong‐Jie Peng,et al.  A Cooperative Interface for Highly Efficient Lithium–Sulfur Batteries , 2016, Advanced materials.

[14]  J. Janek,et al.  Tuning Transition Metal Oxide–Sulfur Interactions for Long Life Lithium Sulfur Batteries: The “Goldilocks” Principle , 2016 .

[15]  Yury Gogotsi,et al.  25th Anniversary Article: MXenes: A New Family of Two‐Dimensional Materials , 2014, Advanced materials.

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

[17]  L. Nazar,et al.  A Nitrogen and Sulfur Dual‐Doped Carbon Derived from Polyrhodanine@Cellulose for Advanced Lithium–Sulfur Batteries , 2015, Advanced materials.

[18]  Zhe Yuan,et al.  Hierarchical Free‐Standing Carbon‐Nanotube Paper Electrodes with Ultrahigh Sulfur‐Loading for Lithium–Sulfur Batteries , 2014 .

[19]  Na Xu,et al.  Molecularly Imprinted Polymer Enables High-Efficiency Recognition and Trapping Lithium Polysulfides for Stable Lithium Sulfur Battery. , 2017, Nano letters.

[20]  A. Manthiram,et al.  Ultra-lightweight PANiNF/MWCNT-functionalized separators with synergistic suppression of polysulfide migration for Li–S batteries with pure sulfur cathodes , 2015 .

[21]  Jingxiang Zhao,et al.  Functional group-dependent anchoring effect of titanium carbide-based MXenes for lithium-sulfur batteries: A computational study , 2017 .

[22]  Guangyuan Zheng,et al.  Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design , 2016, Nature Communications.

[23]  D. Aurbach,et al.  Review on Li‐Sulfur Battery Systems: an Integral Perspective , 2015 .

[24]  Donald J. Siegel,et al.  Tuning the Adsorption of Polysulfides in Lithium–Sulfur Batteries with Metal–Organic Frameworks , 2017 .

[25]  Tingzheng Hou,et al.  An Analogous Periodic Law for Strong Anchoring of Polysulfides on Polar Hosts in Lithium Sulfur Batteries: S- or Li-Binding on First-Row Transition-Metal Sulfides? , 2017 .

[26]  M. Barsoum,et al.  Crystal-chemistry of the Ti3AlC2 and Ti4AlN3 layered carbide/nitride phases—characterization by XPS , 2001 .

[27]  A. Manthiram,et al.  A High Energy Lithium‐Sulfur Battery with Ultrahigh‐Loading Lithium Polysulfide Cathode and its Failure Mechanism , 2016 .

[28]  Jun Lu,et al.  Strong lithium polysulfide chemisorption on electroactive sites of nitrogen-doped carbon composites for high-performance lithium-sulfur battery cathodes. , 2015, Angewandte Chemie.

[29]  J. Tarascon,et al.  Analytical detection of soluble polysulphides in a modified Swagelok cell , 2011 .

[30]  Arumugam Manthiram,et al.  High‐Performance Lithium‐Sulfur Batteries with a Self‐Supported, 3D Li2S‐Doped Graphene Aerogel Cathodes , 2016 .

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

[32]  Yury Gogotsi,et al.  Two-dimensional transition metal carbides. , 2012, ACS nano.

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

[34]  Xiulin Fan,et al.  Tailoring Surface Acidity of Metal Oxide for Better Polysulfide Entrapment in Li‐S Batteries , 2016 .

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

[36]  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.

[37]  Xiaobin Fan,et al.  Sulfonated graphene as water-tolerant solid acid catalyst , 2011 .

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

[39]  Arumugam Manthiram,et al.  Dual‐Confined Flexible Sulfur Cathodes Encapsulated in Nitrogen‐Doped Double‐Shelled Hollow Carbon Spheres and Wrapped with Graphene for Li–S Batteries , 2015 .

[40]  Hong‐Jie Peng,et al.  Enhanced Electrochemical Kinetics on Conductive Polar Mediators for Lithium-Sulfur Batteries. , 2016, Angewandte Chemie.

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

[42]  X. Lou,et al.  Hollow Carbon Nanofibers Filled with MnO2 Nanosheets as Efficient Sulfur Hosts for Lithium-Sulfur Batteries. , 2015, Angewandte Chemie.

[43]  H. Fan,et al.  Prussian Blue Nanocubes with an Open Framework Structure Coated with PEDOT as High‐Capacity Cathodes for Lithium–Sulfur Batteries , 2017, Advanced materials.

[44]  Frank Y. Fan,et al.  Mechanism and Kinetics of Li2S Precipitation in Lithium–Sulfur Batteries , 2015, Advanced materials.

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

[46]  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.

[47]  X. Lou,et al.  Double-Shelled Nanocages with Cobalt Hydroxide Inner Shell and Layered Double Hydroxides Outer Shell as High-Efficiency Polysulfide Mediator for Lithium-Sulfur Batteries. , 2016, Angewandte Chemie.

[48]  Michael J. Tarlov,et al.  Characterization of polydopamine thin films deposited at short times by autoxidation of dopamine. , 2013, Langmuir : the ACS journal of surfaces and colloids.

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

[50]  Weidong Zhou,et al.  Tailoring Pore Size of Nitrogen‐Doped Hollow Carbon Nanospheres for Confining Sulfur in Lithium–Sulfur Batteries , 2015 .

[51]  Guangmin Zhou,et al.  Sulfur confined in nitrogen-doped microporous carbon used in a carbonate-based electrolyte for long-life, safe lithium-sulfur batteries , 2016 .

[52]  Guangmin Zhou,et al.  Understanding the interactions between lithium polysulfides and N-doped graphene using density functional theory calculations , 2016 .

[53]  Jens Tübke,et al.  Development and costs calculation of lithium–sulfur cells with high sulfur load and binder free electrodes , 2013 .

[54]  Zhe Yuan,et al.  Powering Lithium-Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts. , 2016, Nano letters.

[55]  Wei Li,et al.  Rational design of a metal–organic framework host for sulfur storage in fast, long-cycle Li–S batteries , 2014 .

[56]  Weidong Zhou,et al.  Polydopamine-coated, nitrogen-doped, hollow carbon-sulfur double-layered core-shell structure for improving lithium-sulfur batteries. , 2014, Nano letters.

[57]  Yayuan Liu,et al.  An Aqueous Inorganic Polymer Binder for High Performance Lithium–Sulfur Batteries with Flame-Retardant Properties , 2018, ACS central science.

[58]  Guangyuan Zheng,et al.  Understanding the role of different conductive polymers in improving the nanostructured sulfur cathode performance. , 2013, Nano letters.

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

[60]  Dipan Kundu,et al.  Rational design of sulphur host materials for Li-S batteries: correlating lithium polysulphide adsorptivity and self-discharge capacity loss. , 2015, Chemical communications.

[61]  L. Nazar,et al.  Interwoven MXene Nanosheet/Carbon‐Nanotube Composites as Li–S Cathode Hosts , 2017, Advanced materials.