Sulfur/Oxygen Codoped Porous Hard Carbon Microspheres for High‐Performance Potassium‐Ion Batteries

Potassium‐ion batteries (KIBs) are very promising alternatives to lithium‐ion batteries (LIBs) for large‐scale energy storage. However, traditional carbon anode materials usually show poor performance in KIBs due to the large size of K ions. Herein, a carbonization‐etching strategy is reported for making a class of sulfur (S) and oxygen (O) codoped porous hard carbon microspheres (PCMs) material as a novel anode for KIBs through pyrolysis of the polymer microspheres (PMs) composed of a liquid crystal/epoxy monomer/thiol hardener system. The as‐made PCMs possess a porous architecture with a large Brunauer–Emmett–Teller surface area (983.2 m2 g−1), an enlarged interlayer distance (0.393 nm), structural defects induced by the S/O codoping and also amorphous carbon nature. These new features are important for boosting potassium ion storage, allowing the PCMs to deliver a high potassiation capacity of 226.6 mA h g−1 at 50 mA g−1 over 100 cycles and be displaying high stability by showing a potassiation capacity of 108.4 mA h g−1 over 2000 cycles at 1000 mA g−1. The density functional theory calculations demonstrate that S/O codoping not only favors the adsorption of K to the PCMs electrode but also reduces its structural deformation during the potassiation/depotassiation. The present work highlights the important role of hierarchical porosity and S/O codoping in potassium storage.

[1]  C. Han,et al.  Layered Structure Formation in the Reaction-Induced Phase Separation of Epoxy/Polyimide Blends , 2008 .

[2]  Wei Wang,et al.  Short‐Range Order in Mesoporous Carbon Boosts Potassium‐Ion Battery Performance , 2018 .

[3]  Jun Liu,et al.  Sodium ion insertion in hollow carbon nanowires for battery applications. , 2012, Nano letters.

[4]  M. Armand,et al.  Building better batteries , 2008, Nature.

[5]  Jinghua Wu,et al.  Hierarchical VS2 Nanosheet Assemblies: A Universal Host Material for the Reversible Storage of Alkali Metal Ions , 2017, Advanced materials.

[6]  Jie Cai,et al.  A Hierarchical N/S‐Codoped Carbon Anode Fabricated Facilely from Cellulose/Polyaniline Microspheres for High‐Performance Sodium‐Ion Batteries , 2016 .

[7]  Shinichi Komaba,et al.  Research development on sodium-ion batteries. , 2014, Chemical reviews.

[8]  M. Grunze,et al.  Influence of Aromatic Groups Incorporated in Long-Chain Alkanethiol Self-Assembled Monolayers on Gold , 2000 .

[9]  Yunhui Huang,et al.  Sulfur‐Doped Carbon with Enlarged Interlayer Distance as a High‐Performance Anode Material for Sodium‐Ion Batteries , 2015, Advanced science.

[10]  Yi Cui,et al.  Nickel hexacyanoferrate nanoparticle electrodes for aqueous sodium and potassium ion batteries. , 2011, Nano letters.

[11]  Keith Share,et al.  Role of Nitrogen-Doped Graphene for Improved High-Capacity Potassium Ion Battery Anodes. , 2016, ACS nano.

[12]  Clement Bommier,et al.  Hard Carbon Microspheres: Potassium‐Ion Anode Versus Sodium‐Ion Anode , 2016 .

[13]  Y. Liu,et al.  In situ transmission electron microscopy study of electrochemical sodiation and potassiation of carbon nanofibers. , 2014, Nano letters.

[14]  Y. Marcus Thermodynamic functions of transfer of single ions from water to nonaqueous and mixed solvents: Part 3 - Standard potentials of selected electrodes , 1985 .

[15]  Jianhua Li,et al.  Porous epoxy monolith prepared via chemically induced phase separation , 2009 .

[16]  Anubhav Jain,et al.  Voltage, stability and diffusion barrier differences between sodium-ion and lithium-ion intercalation materials , 2011 .

[17]  A. Glushenkov,et al.  Tin-based composite anodes for potassium-ion batteries. , 2016, Chemical communications.

[18]  Wei Wang,et al.  Hard carbon nanoparticles as high-capacity, high-stability anodic materials for Na-ion batteries , 2016 .

[19]  Jianjun Jiang,et al.  Nitrogen-rich hard carbon as a highly durable anode for high-power potassium-ion batteries , 2017 .

[20]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[21]  Kangsheng Huang,et al.  Phosphorus and oxygen dual-doped graphene as superior anode material for room-temperature potassium-ion batteries , 2017 .

[22]  Xiulei Ji,et al.  Emerging Non-Aqueous Potassium-Ion Batteries: Challenges and Opportunities , 2017 .

[23]  A. Glushenkov,et al.  High capacity potassium-ion battery anodes based on black phosphorus , 2017 .

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

[25]  Xiulei Ji,et al.  Polynanocrystalline Graphite: A New Carbon Anode with Superior Cycling Performance for K-Ion Batteries. , 2017, ACS applied materials & interfaces.

[26]  Y. Qian,et al.  Few layer nitrogen-doped graphene with highly reversible potassium storage , 2017 .

[27]  R. D. Shannon Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .

[28]  Xiong Wen Lou,et al.  Sb@C coaxial nanotubes as a superior long-life and high-rate anode for sodium ion batteries , 2016 .

[29]  H. Monkhorst,et al.  SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS , 1976 .

[30]  Javier Pérez-Ramírez,et al.  Pore size determination in modified micro- and mesoporous materials. Pitfalls and limitations in gas adsorption data analysis , 2003 .

[31]  Jun Liu,et al.  Manipulating Adsorption–Insertion Mechanisms in Nanostructured Carbon Materials for High‐Efficiency Sodium Ion Storage , 2017 .

[32]  X. Bao,et al.  Alkalized Ti3C2 MXene nanoribbons with expanded interlayer spacing for high-capacity sodium and potassium ion batteries , 2017 .

[33]  Fan Zhang,et al.  A Dual‐Carbon Battery Based on Potassium‐Ion Electrolyte , 2017 .

[34]  Yubo Fan,et al.  Formation of porous PLGA scaffolds by a combining method of thermally induced phase separation and porogen leaching , 2008 .

[35]  Xiulei Ji,et al.  Potassium Secondary Batteries. , 2017, ACS applied materials & interfaces.

[36]  R. Vaia,et al.  Two-phase nanoscale morphology of polymer/LC composites , 2001 .

[37]  Xiulei Ji,et al.  Carbon Electrodes for K-Ion Batteries. , 2015, Journal of the American Chemical Society.

[38]  A. Manthiram,et al.  Low-Cost High-Energy Potassium Cathode. , 2017, Journal of the American Chemical Society.

[39]  R. Socha,et al.  XPS and NMR studies of phosphoric acid activated carbons , 2008 .

[40]  Martin Winter,et al.  Electrochemical lithiation of tin and tin-based intermetallics and composites , 1999 .

[41]  Xiaodi Ren,et al.  MoS2 as a long-life host material for potassium ion intercalation , 2017, Nano Research.

[42]  J. Pascault,et al.  Thermodynamic analysis of reaction-induced phase separation in epoxy-based polymer dispersed liquid crystals (PDLC) , 1998 .

[43]  Chunsheng Wang,et al.  Electrochemical Intercalation of Potassium into Graphite , 2016 .

[44]  Jean-Marie Tarascon,et al.  Is lithium the new gold? , 2010, Nature chemistry.

[45]  Chem. , 2020, Catalysis from A to Z.

[46]  Blöchl,et al.  Projector augmented-wave method. , 1994, Physical review. B, Condensed matter.

[47]  Haegyeom Kim,et al.  Understanding the Electrochemical Mechanism of the New Iron-Based Mixed-Phosphate Na4Fe3(PO4)2(P2O7) in a Na Rechargeable Battery , 2013 .

[48]  Stefan Grimme,et al.  Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction , 2006, J. Comput. Chem..

[49]  Na Xu,et al.  Ultra‐High Pyridinic N‐Doped Porous Carbon Monolith Enabling High‐Capacity K‐Ion Battery Anodes for Both Half‐Cell and Full‐Cell Applications , 2017, Advanced materials.

[50]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[51]  X. Bao,et al.  Ti3C2 MXene-Derived Sodium/Potassium Titanate Nanoribbons for High-Performance Sodium/Potassium Ion Batteries with Enhanced Capacities. , 2017, ACS nano.

[52]  Adam P. Cohn,et al.  Mechanism of potassium ion intercalation staging in few layered graphene from in situ Raman spectroscopy. , 2016, Nanoscale.

[53]  Zhixin Chen,et al.  Phosphorus-Based Alloy Materials for Advanced Potassium-Ion Battery Anode. , 2017, Journal of the American Chemical Society.

[54]  Ling Fan,et al.  Potassium-Based Dual Ion Battery with Dual-Graphite Electrode. , 2017, Small.

[55]  Jin Han,et al.  Exploration of K2Ti8O17 as an anode material for potassium-ion batteries. , 2016, Chemical communications.

[56]  Xiulei Ji,et al.  Na+ intercalation pseudocapacitance in graphene-coupled titanium oxide enabling ultra-fast sodium storage and long-term cycling , 2015, Nature Communications.

[57]  Andreas Stein,et al.  Porous Electrode Materials for Lithium‐Ion Batteries – How to Prepare Them and What Makes Them Special , 2012 .