A Lithium–Sulfur Battery using a 2D Current Collector Architecture with a Large‐Sized Sulfur Host Operated under High Areal Loading and Low E/S Ratio

While backless freestanding 3D electrode architectures for batteries with high loading sulfur have flourished in the recent years, the more traditional and industrially turnkey 2D architecture has not received the same amount of attention. This work reports a spray-dried sulfur composite with large intrinsic internal pores, ensuring adequate local electrolyte availability. This material offers good performance with a electrolyte content of 7 µL mg-1 at high areal loadings (5-8 mg cm-2 ), while also offering the first reported 2.8 µL mg-1 (8 mg cm-2 ) to enter into the second plateau of discharge and continue to operate for 20 cycles. Moreover, evidence is provided that the high-frequency semicircle (i.e., interfacial resistance) is mainly responsible for the often observed bypassing of the second plateau in lean electrolyte discharges.

[1]  B. L. Gorrec,et al.  First lithiation and charge/discharge cycles of graphite materials, investigated by electrochemical impedance spectroscopy , 2003 .

[2]  C. Villevieille,et al.  Direct observation of lithium polysulfides in lithium–sulfur batteries using operando X-ray diffraction , 2017, Nature Energy.

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

[4]  Zhian Zhang,et al.  Electrochemical Impedance Spectroscopy Study of a Lithium/Sulfur Battery: Modeling and Analysis of Capacity Fading , 2013 .

[5]  A. Yu,et al.  Structural and chemical synergistic encapsulation of polysulfides enables ultralong-life lithium–sulfur batteries , 2016 .

[6]  Huamin Zhang,et al.  Lithium Sulfur Primary Battery with Super High Energy Density: Based on the Cauliflower-like Structured C/S Cathode , 2015, Scientific Reports.

[7]  Jianming Zheng,et al.  Behavior of Lithium Metal Anodes under Various Capacity Utilization and High Current Density in Lithium Metal Batteries , 2017 .

[8]  Xueliang Sun,et al.  Structural Design of Lithium–Sulfur Batteries: From Fundamental Research to Practical Application , 2018, Electrochemical Energy Reviews.

[9]  Jens Tübke,et al.  Lithium–Sulfur Cells: The Gap between the State‐of‐the‐Art and the Requirements for High Energy Battery Cells , 2015 .

[10]  Dean J. Miller,et al.  Burning lithium in CS2 for high-performing compact Li2S–graphene nanocapsules for Li–S batteries , 2017, Nature Energy.

[11]  J. Moon,et al.  Spherical Macroporous Carbon Nanotube Particles with Ultrahigh Sulfur Loading for Lithium-Sulfur Battery Cathodes. , 2018, ACS nano.

[12]  Moses Ender,et al.  Separation of Charge Transfer and Contact Resistance in LiFePO4-Cathodes by Impedance Modeling , 2012 .

[13]  J. Choi,et al.  Hierarchical porous carbon by ultrasonic spray pyrolysis yields stable cycling in lithium-sulfur battery. , 2014, Nano letters.

[14]  L. James Wright,et al.  Cover Picture: A Metallaanthracene and Derived Metallaanthraquinone (Angew. Chem. Int. Ed. 1/2017) , 2017 .

[15]  Jun Lu,et al.  Chemisorption of polysulfides through redox reactions with organic molecules for lithium–sulfur batteries , 2018, Nature Communications.

[16]  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 .

[17]  Matthew Li,et al.  Compact high volumetric and areal capacity lithium sulfur batteries through rock salt induced nano-architectured sulfur hosts , 2017 .

[18]  F. Üstel,et al.  Spray drying of hydroxyapatite powders: The effect of spray drying parameters and heat treatment on the particle size and morphology , 2017 .

[19]  E. Cairns,et al.  Freeze-Dried Sulfur-Graphene Oxide-Carbon Nanotube Nanocomposite for High Sulfur-Loading Lithium/Sulfur Cells. , 2017, Nano letters.

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

[21]  Qiang Zhang,et al.  Popcorn Inspired Porous Macrocellular Carbon: Rapid Puffing Fabrication from Rice and Its Applications in Lithium–Sulfur Batteries , 2018 .

[22]  Kun Feng,et al.  Gas Pickering Emulsion Templated Hollow Carbon for High Rate Performance Lithium Sulfur Batteries , 2016 .

[23]  A. Dasari,et al.  Chemical and thermal reduction of graphene oxide and its electrically conductive polylactic acid nanocomposites , 2012 .

[24]  Hee‐Tak Kim,et al.  Binary electrolyte based on tetra(ethylene glycol) dimethyl ether and 1,3-dioxolane for lithium-sulfur battery , 2002 .

[25]  Zhengcheng Zhang,et al.  Understanding the effect of a fluorinated ether on the performance of lithium-sulfur batteries. , 2015, ACS applied materials & interfaces.

[26]  Zhongwei Chen,et al.  Interaction mechanism between a functionalized protective layer and dissolved polysulfide for extended cycle life of lithium sulfur batteries , 2015 .

[27]  Wen Lei,et al.  Stringed “tube on cube” nanohybrids as compact cathode matrix for high-loading and lean-electrolyte lithium–sulfur batteries , 2018 .

[28]  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.

[29]  Yong‐Sheng Hu,et al.  Novel Large‐Scale Synthesis of a C/S Nanocomposite with Mixed Conducting Networks through a Spray Drying Approach for Li–S Batteries , 2015 .

[30]  D. Beljonne,et al.  How Methylammonium Cations and Chlorine Dopants Heal Defects in Lead Iodide Perovskites , 2018 .

[31]  Shubin Yang,et al.  Vertically aligned sulfur-graphene nanowalls on substrates for ultrafast lithium-sulfur batteries. , 2015, Nano letters.

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

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

[34]  Jun Lu,et al.  Encapsulating Various Sulfur Allotropes within Graphene Nanocages for Long‐Lasting Lithium Storage , 2018 .

[35]  Jun Liu,et al.  Improving Lithium-Sulfur Battery Performance under Lean Electrolyte through Nanoscale Confinement in Soft Swellable Gels. , 2017, Nano letters.

[36]  Jim P. Zheng,et al.  Communication—Effect of Lithium Polysulfide Solubility on Capacity of Lithium-Sulfur Cells , 2017 .

[37]  Arumugam Manthiram,et al.  Rational Design of Statically and Dynamically Stable Lithium–Sulfur Batteries with High Sulfur Loading and Low Electrolyte/Sulfur Ratio , 2018, Advanced materials.

[38]  M. Fowler,et al.  Multi-Particle Model for a Commercial Blended Lithium-Ion Electrode , 2016 .

[39]  W. Klemm,et al.  Über einige neuere Ergebnisse der anorganischen Chemie , 1943 .

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

[41]  Wen Lei,et al.  3D Porous Carbon Sheets with Multidirectional Ion Pathways for Fast and Durable Lithium–Sulfur Batteries , 2018 .

[42]  A. Yu,et al.  Sulfur Nanogranular Film-Coated Three-Dimensional Graphene Sponge-Based High Power Lithium Sulfur Battery. , 2016, ACS applied materials & interfaces.

[43]  E. W. Washburn The Dynamics of Capillary Flow , 1921 .

[44]  Yet-Ming Chiang,et al.  Electrodeposition Kinetics in Li-S Batteries: Effects of Low Electrolyte/Sulfur Ratios and Deposition Surface Composition , 2017 .

[45]  Jun Lu,et al.  Lithium-Sulfur Batteries for Commercial Applications , 2018 .

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

[47]  C. Tropea,et al.  Study of the internal flow in a rotary atomizer and its influence on the properties of the resulting spray , 2017 .

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

[49]  Taeeun Yim,et al.  Effective Polysulfide Rejection by Dipole‐Aligned BaTiO3 Coated Separator in Lithium–Sulfur Batteries , 2016 .