A 3D Nitrogen‐Doped Graphene/TiN Nanowires Composite as a Strong Polysulfide Anchor for Lithium–Sulfur Batteries with Enhanced Rate Performance and High Areal Capacity

Lithium–sulfur (Li–S) batteries have attracted remarkable attention due to their high theoretical capacity of 1675 mAh g−1, rich resources, inexpensiveness, and environmental friendliness. However, the practical application of the Li–S battery is hindered by the shuttling of soluble lithium polysulfides (LiPSs) and slow redox reactions. Herein, a 3D nitrogen‐doped graphene/titanium nitride nanowires (3DNG/TiN) composite is reported as a freestanding electrode for Li–S batteries. The highly porous conductive graphene network provides efficient pathways for both electrons and ions. TiN nanowires attached on the graphene sheets have a strong chemical anchor effect on the polysulfides, which is proved by the superior performance and by density functional theory calculations. As a result, the 3DNG/TiN cathode exhibits an initial capacity of 1510 mAh g−1 and the capacity remains at 1267 mAh g−1 after 100 cycles at 0.5 C. Even at 5 C, a capacity of 676 mAh g−1 is reached. With a high sulfur loading of 9.6 mg cm−2, the 3DNG cathode achieves an ultrahigh areal capacity of 12.0 mAh cm−2 at a high current density of 8.03 mA cm−2. This proposed unique structure gives a bright prospect in that high energy density and high power density can be achieved simultaneously for Li–S batteries.

[1]  C. Niu,et al.  The lithium and sodium storage performances of phosphorus and its hierarchical structure , 2018, Nano Research.

[2]  Jingyu Sun,et al.  In Situ Assembly of 2D Conductive Vanadium Disulfide with Graphene as a High‐Sulfur‐Loading Host for Lithium–Sulfur Batteries , 2018 .

[3]  Huamin Zhang,et al.  Anchor and activate sulfide with LiTi2(PO4)2.88F0.12 nano spheres for lithium sulfur battery application , 2018 .

[4]  K. Ng,et al.  Structured Titanium Nitride Nanotube Arrays/Sulfur Composite as Cathode Materials for Advanced Lithium Sulfur Battery , 2018 .

[5]  Feng Wu,et al.  Three-Dimensional Carbon Current Collector Promises Small Sulfur Molecule Cathode with High Areal Loading for Lithium-Sulfur Batteries. , 2018, ACS applied materials & interfaces.

[6]  Quan-hong Yang,et al.  Catalyzing polysulfide conversion by g-C3N4 in a graphene network for long-life lithium-sulfur batteries , 2018, Nano Research.

[7]  A. Manthiram,et al.  TiS2–Polysulfide Hybrid Cathode with High Sulfur Loading and Low Electrolyte Consumption for Lithium–Sulfur Batteries , 2018 .

[8]  A. Manthiram,et al.  Covalently Grafted Polysulfur–Graphene Nanocomposites for Ultrahigh Sulfur-Loading Lithium–Polysulfur Batteries , 2018 .

[9]  Qiang Zhang,et al.  Review on High‐Loading and High‐Energy Lithium–Sulfur Batteries , 2017 .

[10]  Wenjun Zhang,et al.  Porous-Shell Vanadium Nitride Nanobubbles with Ultrahigh Areal Sulfur Loading for High-Capacity and Long-Life Lithium-Sulfur Batteries. , 2017, Nano letters.

[11]  Jeng‐Kuei Chang,et al.  A Honeycomb-like Co@N-C Composite for Ultrahigh Sulfur Loading Li-S Batteries. , 2017, ACS nano.

[12]  A. Manthiram,et al.  Rational Design of High-Loading Sulfur Cathodes with a Poached-Egg-Shaped Architecture for Long-Cycle Lithium–Sulfur Batteries , 2017 .

[13]  Yuxi Xu,et al.  Integration of Graphene, Nano Sulfur, and Conducting Polymer into Compact, Flexible Lithium–Sulfur Battery Cathodes with Ultrahigh Volumetric Capacity and Superior Cycling Stability for Foldable Devices , 2017, Advanced materials.

[14]  Guangmin Zhou,et al.  Twinborn TiO2–TiN heterostructures enabling smooth trapping–diffusion–conversion of polysulfides towards ultralong life lithium–sulfur batteries , 2017 .

[15]  M. Zheng,et al.  Co4N Nanosheet Assembled Mesoporous Sphere as a Matrix for Ultrahigh Sulfur Content Lithium-Sulfur Batteries. , 2017, ACS nano.

[16]  Rongming Wang,et al.  Freestanding and Sandwich‐Structured Electrode Material with High Areal Mass Loading for Long‐Life Lithium–Sulfur Batteries , 2017 .

[17]  Qiang Zhang,et al.  Nanostructured Metal Oxides and Sulfides for Lithium–Sulfur Batteries , 2017, Advanced materials.

[18]  Guoxiu Wang,et al.  Fabrication of N‐doped Graphene–Carbon Nanotube Hybrids from Prussian Blue for Lithium–Sulfur Batteries , 2017 .

[19]  Feng Li,et al.  Conductive porous vanadium nitride/graphene composite as chemical anchor of polysulfides for lithium-sulfur batteries , 2017, Nature Communications.

[20]  L. Nazar,et al.  A Comprehensive Approach toward Stable Lithium–Sulfur Batteries with High Volumetric Energy Density , 2017 .

[21]  Yayuan Liu,et al.  Catalytic oxidation of Li2S on the surface of metal sulfides for Li−S batteries , 2017, Proceedings of the National Academy of Sciences.

[22]  Yousung Jung,et al.  Heterogeneous Catalysis for Lithium–Sulfur Batteries: Enhanced Rate Performance by Promoting Polysulfide Fragmentations , 2017 .

[23]  Jingwei Xiang,et al.  TiN as a simple and efficient polysulfide immobilizer for lithium–sulfur batteries , 2016 .

[24]  Guoxiu Wang,et al.  3D Metal Carbide@Mesoporous Carbon Hybrid Architecture as a New Polysulfide Reservoir for Lithium‐Sulfur Batteries , 2016 .

[25]  A. Manthiram,et al.  A Carbon-Cotton Cathode with Ultrahigh-Loading Capability for Statically and Dynamically Stable Lithium-Sulfur Batteries. , 2016, ACS nano.

[26]  Xueliang Li,et al.  Hierarchical Porous Carbon Aerogels with VN Modification as Cathode Matrix for High Performance Lithium-Sulfur Batteries , 2016 .

[27]  A. Manthiram,et al.  Mesoporous Titanium Nitride‐Enabled Highly Stable Lithium‐Sulfur Batteries , 2016, Advanced materials.

[28]  S. Salley,et al.  Nanostructured titanium nitride as a novel cathode for high performance lithium/dissolved polysulfide batteries , 2016 .

[29]  Mi-Dan Cao,et al.  VN hollow spheres assembled from porous nanosheets for high-performance lithium storage and the oxygen reduction reaction , 2016 .

[30]  Ruopian Fang,et al.  3D Interconnected Electrode Materials with Ultrahigh Areal Sulfur Loading for Li–S Batteries , 2016, Advanced materials.

[31]  Xiaojing Zhao,et al.  From Hollow Carbon Spheres to N‐Doped Hollow Porous Carbon Bowls: Rational Design of Hollow Carbon Host for Li‐S Batteries , 2016 .

[32]  L. Nazar,et al.  In Situ Reactive Assembly of Scalable Core-Shell Sulfur-MnO2 Composite Cathodes. , 2016, ACS nano.

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

[34]  Dipan Kundu,et al.  A graphene-like metallic cathode host for long-life and high-loading lithium–sulfur batteries , 2016 .

[35]  Yong Huang,et al.  Three-dimensional porous carbon composites containing high sulfur nanoparticle content for high-performance lithium–sulfur batteries , 2016, Nature Communications.

[36]  Yihe Zhang,et al.  Sulfur Embedded in a Mesoporous Carbon Nanotube Network as a Binder-Free Electrode for High-Performance Lithium-Sulfur Batteries. , 2016, ACS nano.

[37]  Feixiang Wu,et al.  Graphene-Li2S-Carbon Nanocomposite for Lithium-Sulfur Batteries. , 2016, ACS nano.

[38]  M. Delville,et al.  Controlling Disorder and Superconductivity in Titanium Oxynitride Nanoribbons with Anion Exchange. , 2015, ACS nano.

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

[40]  Shaoming Huang,et al.  A Lightweight TiO2/Graphene Interlayer, Applied as a Highly Effective Polysulfide Absorbent for Fast, Long‐Life Lithium–Sulfur Batteries , 2015, Advanced materials.

[41]  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.

[42]  Jun Chen,et al.  Sulfur nanodots electrodeposited on ni foam as high-performance cathode for Li-S batteries. , 2015, Nano letters.

[43]  Xin-Bing Cheng,et al.  Electrodes: Hierarchical Free‐Standing Carbon‐Nanotube Paper Electrodes with Ultrahigh Sulfur‐Loading for Lithium–Sulfur Batteries (Adv. Funct. Mater. 39/2014) , 2014 .

[44]  Yi Cui,et al.  Sulfur cathodes with hydrogen reduced titanium dioxide inverse opal structure. , 2014, ACS Nano.

[45]  L. Nazar,et al.  Lithium-sulfur batteries , 2014 .

[46]  Fan Zhang,et al.  Sulfur-infiltrated graphene-based layered porous carbon cathodes for high-performance lithium-sulfur batteries. , 2014, ACS nano.

[47]  Donghai Wang,et al.  Nitrogen‐Doped Mesoporous Carbon Promoted Chemical Adsorption of Sulfur and Fabrication of High‐Areal‐Capacity Sulfur Cathode with Exceptional Cycling Stability for Lithium‐Sulfur Batteries , 2014 .

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

[49]  Lixia Yuan,et al.  Insight into the Electrode Mechanism in Lithium‐Sulfur Batteries with Ordered Microporous Carbon Confined Sulfur as the Cathode , 2013 .

[50]  Guangyuan Zheng,et al.  Sulphur–TiO2 yolk–shell nanoarchitecture with internal void space for long-cycle lithium–sulphur batteries , 2013, Nature Communications.

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

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

[53]  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.

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

[55]  Jinghua Guo,et al.  Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells. , 2011, Journal of the American Chemical Society.