High-strength graphene composite films by molecular level couplings for flexible supercapacitors with high volumetric capacitance

A critical challenge in fabricating the electrodes of flexible supercapacitors is to optimize their electrochemical performance without deteriorating their mechanical properties. We report here a strategy to prepare freestanding reduced graphene oxide@polyvinyl alcohol (rGO@PVA) composite films by synchronously reducing and assembling GO sheets with PVA molecules on a metal surface. Such rGO@PVA composite films realize the controllable assembly of rGO sheets and PVA in an ordered layered structure as well as the molecular level couplings between rGO sheets and PVA molecules. As a result, the rGO@PVA composite films display extremely high strength and Young's modulus. After introducing H2SO4, the PVA/H2SO4 electrolyte layer between rGO sheets can form fast ion transport channel at the molecular level in the composite films. Therefore, the composite films deliver high volumetric capacity (206.8 F cm−3), excellent energy density (7.18 mW h cm−3) and power density (2.92 W cm−3). More importantly, the supercapacitors based on the composite films show stable electrochemical performance under different stresses and bending states, even when the supercapacitors were bent to 180°. The high flexibility and electrochemical performance of such supercapacitors will enable a broad field of energy-storage devices to be compatible with flexible and wearable electronics.

[1]  Renming Liu,et al.  Surface-enhanced Raman scattering study of human serum on PVAAg nanofilm prepared by using electrostatic self-assembly , 2011 .

[2]  C. Daneault,et al.  Chemical Modification of Poly(Vinyl Alcohol) in Water , 2015 .

[3]  Yang Wang,et al.  A Simple Approach to Boost Capacitance: Flexible Supercapacitors Based on Manganese Oxides@MOFs via Chemically Induced In Situ Self‐Transformation , 2016, Advanced materials.

[4]  Chun Huang,et al.  Solid-state supercapacitors with rationally designed heterogeneous electrodes fabricated by large area spray processing for wearable energy storage applications , 2016, Scientific Reports.

[5]  M. Khenfouch,et al.  Tuning the luminescence and optical properties of graphene oxide and reduced graphene oxide functionnalized with PVA , 2016 .

[6]  Fang Qian,et al.  Supercapacitors Based on Three-Dimensional Hierarchical Graphene Aerogels with Periodic Macropores. , 2016, Nano letters.

[7]  Xiaodong Chen,et al.  Electrophoretic build-up of alternately multilayered films and micropatterns based on graphene sheets and nanoparticles and their applications in flexible supercapacitors. , 2012, Small.

[8]  Satish Kumar,et al.  Making Strong Fibers , 2008, Science.

[9]  F. Kang,et al.  Laser-processed graphene based micro-supercapacitors for ultrathin, rollable, compact and designable energy storage components , 2016 .

[10]  Bin Liu,et al.  Fiber-based flexible all-solid-state asymmetric supercapacitors for integrated photodetecting system. , 2014, Angewandte Chemie.

[11]  Y. Badr,et al.  Raman Spectroscopic Study of CdS, PVA Composite Films , 2004 .

[12]  Xin Wang,et al.  Recent progress on graphene-based hybrid electrocatalysts , 2014 .

[13]  M. El‐Kady,et al.  Laser Scribing of High-Performance and Flexible Graphene-Based Electrochemical Capacitors , 2012, Science.

[14]  A. Vijayaraghavan,et al.  Biomimetic Phospholipid Membrane Organization on Graphene and Graphene Oxide Surfaces: A Molecular Dynamics Simulation Study. , 2017, ACS nano.

[15]  Aleksei Aksimentiev,et al.  Graphene Nanopores for Protein Sequencing , 2016, Advanced functional materials.

[16]  Steven W. Cranford,et al.  Tuning the mechanical properties of graphene oxide paper and its associated polymer nanocomposites by controlling cooperative intersheet hydrogen bonding. , 2012, ACS nano.

[17]  Cheng Yang,et al.  Shape-Tailorable Graphene-Based Ultra-High-Rate Supercapacitor for Wearable Electronics. , 2015, ACS nano.

[18]  G. Shi,et al.  Multifunctional Pristine Chemically Modified Graphene Films as Strong as Stainless Steel , 2015, Advanced materials.

[19]  O. Wolfbeis,et al.  A Phytic Acid Induced Super-Amphiphilic Multifunctional 3D Graphene-Based Foam. , 2016, Angewandte Chemie.

[20]  Jun Chen,et al.  A Flexible Nanostructured Paper of a Reduced Graphene Oxide–Sulfur Composite for High‐Performance Lithium–Sulfur Batteries with Unconventional Configurations , 2016, Advanced materials.

[21]  R. Sun,et al.  Flexible Asymmetrical Solid-State Supercapacitors Based on Laboratory Filter Paper. , 2016, ACS nano.

[22]  M. Maugey,et al.  Raman Response of Carbon Nanotube/PVA Fibers under Strain , 2009 .

[23]  Uday Narayan Maiti,et al.  Three‐Dimensional Shape Engineered, Interfacial Gelation of Reduced Graphene Oxide for High Rate, Large Capacity Supercapacitors , 2014, Advanced materials.

[24]  M. Oschatz,et al.  Tailoring porosity in carbon materials for supercapacitor applications , 2014 .

[25]  Tianyi Yang,et al.  Bio‐Inspired Nacre‐like Composite Films Based on Graphene with Superior Mechanical, Electrical, and Biocompatible Properties , 2012, Advanced materials.

[26]  Peihua Huang,et al.  On-chip and freestanding elastic carbon films for micro-supercapacitors , 2016, Science.

[27]  Lili Liu,et al.  Nanostructured Graphene Composite Papers for Highly Flexible and Foldable Supercapacitors , 2014, Advanced materials.

[28]  L. Brinson,et al.  High‐Nanofiller‐Content Graphene Oxide–Polymer Nanocomposites via Vacuum‐Assisted Self‐Assembly , 2010 .

[29]  Shuhong Yu,et al.  Flexible graphene–polyaniline composite paper for high-performance supercapacitor , 2013 .

[30]  K. Cen,et al.  Emerging energy and environmental applications of vertically-oriented graphenes. , 2015, Chemical Society reviews.

[31]  P. Taberna,et al.  Electrochemical Characteristics and Impedance Spectroscopy Studies of Carbon-Carbon Supercapacitors , 2003 .

[32]  Zijian Zheng,et al.  Wearable energy-dense and power-dense supercapacitor yarns enabled by scalable graphene–metallic textile composite electrodes , 2015, Nature Communications.

[33]  Xin Wang,et al.  Graphene−Metal Particle Nanocomposites , 2008 .

[34]  A. Matvienko,et al.  Study of PVA thermal destruction by means of IR and Raman spectroscopy , 2010 .

[35]  Jayan Thomas,et al.  Supercapacitor electrode materials: nanostructures from 0 to 3 dimensions , 2015 .

[36]  L. Qu,et al.  A Large‐Area, Flexible, and Flame‐Retardant Graphene Paper , 2016 .

[37]  D. Zhao,et al.  Carbon Materials for Chemical Capacitive Energy Storage , 2011, Advanced materials.

[38]  Lei Zhang,et al.  A review of electrode materials for electrochemical supercapacitors. , 2012, Chemical Society reviews.

[39]  A. Manthiram,et al.  Highly flexible, freestanding tandem sulfur cathodes for foldable Li–S batteries with a high areal capacity , 2017 .

[40]  G. Shi,et al.  Strong and ductile poly(vinyl alcohol)/graphene oxide composite films with a layered structure , 2009 .

[41]  M. El‐Kady,et al.  Graphene-based materials for flexible supercapacitors. , 2015, Chemical Society reviews.

[42]  Jinzhu Li,et al.  High‐Strength Laminated Copper Matrix Nanocomposites Developed from a Single‐Walled Carbon Nanotube Film with Continuous Reticulate Architecture , 2012 .

[43]  Yongyao Xia,et al.  Electrochemical capacitors: mechanism, materials, systems, characterization and applications. , 2016, Chemical Society reviews.

[44]  Jun Chen,et al.  A Leavening Strategy to Prepare Reduced Graphene Oxide Foams , 2012, Advanced materials.

[45]  Ludwig J. Gauckler,et al.  Bioinspired Design and Assembly of Platelet Reinforced Polymer Films , 2008, Science.

[46]  Shiv k. Sharma,et al.  Raman spectral study of solid and dissolved poly(vinyl alcohol) and ethylene-vinyl alcohol copolymer , 1994 .

[47]  H. Nishihara,et al.  Porous Carbon Fibers Containing Pores with Sizes Controlled at the Ångstrom Level by the Cavity Size of Pillar[6]arene. , 2015, Angewandte Chemie.

[48]  S. Stankovich,et al.  Graphene-based composite materials , 2006, Nature.

[49]  Zhiyuan Xiong,et al.  Mechanically Tough Large‐Area Hierarchical Porous Graphene Films for High‐Performance Flexible Supercapacitor Applications , 2015, Advanced materials.

[50]  Seunghwa Ryu,et al.  Graphene-coated meshes for electroactive flow control devices utilizing two antagonistic functions of repellency and permeability , 2016, Nature Communications.

[51]  A. Waas,et al.  Ultrastrong and Stiff Layered Polymer Nanocomposites , 2007, Science.

[52]  Yongsheng Hu,et al.  A repeated halving approach to fabricate ultrathin single-walled carbon nanotube films for transparent supercapacitors. , 2013, Small.

[53]  Junwu Zhu,et al.  Bioinspired Effective Prevention of Restacking in Multilayered Graphene Films: Towards the Next Generation of High‐Performance Supercapacitors , 2011, Advanced materials.

[54]  Xingxiang Zhang,et al.  Continuously hierarchical nanoporous graphene film for flexible solid-state supercapacitors with excellent performance , 2016 .

[55]  A. Hirata,et al.  Bicontinuous nanotubular graphene–polypyrrole hybrid for high performance flexible supercapacitors , 2016 .

[56]  Luqi Liu,et al.  High mechanical performance of layered graphene oxide/poly(vinyl alcohol) nanocomposite films. , 2013, Small.

[57]  Yaping Zang,et al.  Advances of flexible pressure sensors toward artificial intelligence and health care applications , 2015 .

[58]  Xiaosu Yi,et al.  High-strength composite fibers: realizing true potential of carbon nanotubes in polymer matrix through continuous reticulate architecture and molecular level couplings. , 2009, Nano letters.

[59]  Teng Zhai,et al.  H‐TiO2@MnO2//H‐TiO2@C Core–Shell Nanowires for High Performance and Flexible Asymmetric Supercapacitors , 2013, Advanced materials.

[60]  Xiaodong Chen,et al.  Ambient Fabrication of Large‐Area Graphene Films via a Synchronous Reduction and Assembly Strategy , 2013, Advanced materials.

[61]  Tsu-Wei Chou,et al.  High-Strength Single-Walled Carbon Nanotube/Permalloy Nanoparticle/Poly(vinyl alcohol) Multifunctional Nanocomposite Fiber. , 2015, ACS nano.

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

[63]  S. Selvasekarapandian,et al.  Laser Raman and ac impedance spectroscopic studies of PVA: NH4NO3 polymer electrolyte. , 2010, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[64]  Yu Huang,et al.  Holey graphene frameworks for highly efficient capacitive energy storage , 2014, Nature Communications.

[65]  Yu Huang,et al.  Flexible solid-state supercapacitors based on three-dimensional graphene hydrogel films. , 2013, ACS nano.

[66]  Wen Chen,et al.  Polypyrrole-coated paper for flexible solid-state energy storage , 2013 .