Role of Oxygen Functional Groups in Carbon Nanotube/Graphene Freestanding Electrodes for High Performance Lithium Batteries

Hierarchical functionalized multiwalled carbon nanotube (MWNT)/graphene structures with thicknesses up to tens of micrometers and relatively high density (>1 g cm−3) are synthesized using vacuum filtration for the positive electrode of lithium batteries. These electrodes, which are self‐standing and free of binder and current collectors, utilize oxygen functional groups for Faradaic reactions in addition to double‐layer charging, which can impart high gravimetric (230 Wh kg−1 at 2.6 kW kg−1) and volumetric (450 Wh L−1 at 5 kW L−1) performance. It is demonstrated that the gravimetric and volumetric capacity, capacitance, and energy density can be tuned by selective removal of oxygen species from as‐prepared functionalized MWNT/graphene structures with heat treatments in H2/Ar, potentially opening new pathways for the design of electrodes with controlled surface chemistry.

[1]  K. J. Hüttinger,et al.  Surface-oxidized carbon fibers: I. Surface structure and chemistry , 1996 .

[2]  Jacek Klinowski,et al.  Structure of Graphite Oxide Revisited , 1998 .

[3]  P. J. Ollivier,et al.  Layer-by-Layer Assembly of Ultrathin Composite Films from Micron-Sized Graphite Oxide Sheets and Polycations , 1999 .

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

[5]  E. Frąckowiak,et al.  Effect of nitrogen in carbon electrode on the supercapacitor performance , 2005 .

[6]  V. Ruiz,et al.  Activated carbon produced from Sasol-Lurgi gasifier pitch and its application as electrodes in supercapacitors , 2006 .

[7]  P. Taberna,et al.  Anomalous Increase in Carbon Capacitance at Pore Sizes Less Than 1 Nanometer , 2006, Science.

[8]  S. Stankovich,et al.  Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly(sodium 4-styrenesulfonate) , 2006 .

[9]  K. Hata,et al.  Shape-engineerable and highly densely packed single-walled carbon nanotubes and their application as super-capacitor electrodes , 2006, Nature materials.

[10]  S. Stankovich,et al.  Preparation and characterization of graphene oxide paper , 2007, Nature.

[11]  S. Stankovich,et al.  Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide , 2007 .

[12]  E. Frąckowiak.  Carbon materials for supercapacitor application. , 2007, Physical chemistry chemical physics : PCCP.

[13]  R. Ruoff,et al.  Graphene-based ultracapacitors. , 2008, Nano letters.

[14]  Wei Xia,et al.  Thermal Stability and Reducibility of Oxygen-Containing Functional Groups on Multiwalled Carbon Nanotube Surfaces: A Quantitative High-Resolution XPS and TPD/TPR Study , 2008 .

[15]  Y. Gogotsi,et al.  Materials for electrochemical capacitors. , 2008, Nature materials.

[16]  G. Wallace,et al.  Processable aqueous dispersions of graphene nanosheets. , 2008, Nature nanotechnology.

[17]  Pierre-Louis Taberna,et al.  Desolvation of ions in subnanometer pores and its effect on capacitance and double-layer theory. , 2008, Angewandte Chemie.

[18]  Yongsheng Chen,et al.  SUPERCAPACITOR DEVICES BASED ON GRAPHENE MATERIALS , 2009 .

[19]  Yi Cui,et al.  Highly conductive paper for energy-storage devices , 2009, Proceedings of the National Academy of Sciences.

[20]  Shuo Chen,et al.  Layer-by-layer assembly of all carbon nanotube ultrathin films for electrochemical applications. , 2009, Journal of the American Chemical Society.

[21]  Lili Zhang,et al.  Carbon-based materials as supercapacitor electrodes. , 2009, Chemical Society reviews.

[22]  G. Lu,et al.  Fabrication of Graphene/Polyaniline Composite Paper via In Situ Anodic Electropolymerization for High-Performance Flexible Electrode. , 2009, ACS nano.

[23]  Peihua Huang,et al.  Ultrahigh-power micrometre-sized supercapacitors based on onion-like carbon. , 2010, Nature nanotechnology.

[24]  Anran Liu,et al.  Supercapacitors based on flexible graphene/polyaniline nanofiber composite films. , 2010, ACS nano.

[25]  Chang Ming Li,et al.  Layered graphene/quantum dots for photovoltaic devices. , 2010, Angewandte Chemie.

[26]  Shuo Chen,et al.  High-power lithium batteries from functionalized carbon-nanotube electrodes. , 2010, Nature nanotechnology.

[27]  L. Brinson,et al.  Electrically Conductive “Alkylated” Graphene Paper via Chemical Reduction of Amine‐Functionalized Graphene Oxide Paper , 2010, Advanced materials.

[28]  G. Graff,et al.  Ternary self-assembly of ordered metal oxide-graphene nanocomposites for electrochemical energy storage. , 2010, ACS nano.

[29]  P. Taberna,et al.  Monolithic Carbide-Derived Carbon Films for Micro-Supercapacitors , 2010, Science.

[30]  Takeo Yamada,et al.  Extracting the Full Potential of Single‐Walled Carbon Nanotubes as Durable Supercapacitor Electrodes Operable at 4 V with High Power and Energy Density , 2010, Advanced materials.

[31]  Norbert Fabre,et al.  Elaboration of a microstructured inkjet-printed carbon electrochemical capacitor , 2010 .

[32]  Dingshan Yu,et al.  Self-Assembled Graphene/Carbon Nanotube Hybrid Films for Supercapacitors , 2010 .

[33]  Yang Shao-Horn,et al.  Nanostructured carbon-based electrodes: bridging the gap between thin-film lithium-ion batteries and electrochemical capacitors , 2011 .

[34]  Y. Shao-horn,et al.  Thin films of carbon nanotubes and chemically reduced graphenes for electrochemical micro-capacitors , 2011 .

[35]  C. M. Li,et al.  A self-assembled hierarchical nanostructure comprising carbon spheres and graphene nanosheets for enhanced supercapacitor performance , 2011 .

[36]  Y. Shao-horn,et al.  Layer-by-layer assembled polyaniline nanofiber/multiwall carbon nanotube thin film electrodes for high-power and high-energy storage applications. , 2011, ACS nano.

[37]  R. Ruoff,et al.  Carbon-Based Supercapacitors Produced by Activation of Graphene , 2011, Science.

[38]  E. Frąckowiak,et al.  Carbon nanotubes and their composites in electrochemical applications , 2011 .

[39]  Yuki Yamada,et al.  Self-standing positive electrodes of oxidized few-walled carbon nanotubes for light-weight and high-power lithium batteries , 2012 .