Molecular Functionalization of Graphene Oxide for Next-Generation Wearable Electronics.

Acquiring reliable and efficient wearable electronics requires the development of flexible electrolyte membranes (EMs) for energy storage systems with high performance and minimum dependency on the operating conditions. Herein, a freestanding graphene oxide (GO) EM is functionalized with 1-hexyl-3-methylimidazolium chloride (HMIM) molecules via both covalent and noncovalent bonds induced by esterification reactions and electrostatic πcation-π stacking, respectively. Compared to the commercial polymeric membrane, the thin HMIM/GO membrane demonstrates not only slightest performance sensitivity to the operating conditions but also a superior hydroxide conductivity of 0.064 ± 0.0021 S cm(-1) at 30% RH and room temperature, which was 3.8 times higher than that of the commercial membrane at the same conditions. To study the practical application of the HMIM/GO membranes in wearable electronics, a fully solid-state, thin, flexible zinc-air battery and supercapacitor are made exhibiting high battery performance and capacitance at low humidified and room temperature environment, respectively, favored by the bonded HMIM molecules on the surface of GO nanosheets. The results of this study disclose the strong potential of manipulating the chemical structure of GO to work as a lightweight membrane in wearable energy storage devices, possessing highly stable performance at different operating conditions, especially at low relative humidity and room temperature.

[1]  Huisheng Peng,et al.  Flexible, Stretchable, and Rechargeable Fiber-Shaped Zinc-Air Battery Based on Cross-Stacked Carbon Nanotube Sheets. , 2015, Angewandte Chemie.

[2]  Byung Chul Kim,et al.  Recent Progress in Flexible Electrochemical Capacitors: Electrode Materials, Device Configuration, and Functions , 2015 .

[3]  P. Ajayan,et al.  Design Considerations for Unconventional Electrochemical Energy Storage Architectures , 2015 .

[4]  G. Jiang,et al.  Quaternized graphene oxide nanocomposites as fast hydroxide conductors. , 2015, ACS nano.

[5]  Minjoon Park,et al.  All‐Solid‐State Cable‐Type Flexible Zinc–Air Battery , 2015, Advanced materials.

[6]  O. Penkov,et al.  Preparation and characterization of graphene , 2020, Tribology of Graphene.

[7]  Yushan Yan,et al.  Hydroxide Exchange Membranes and Ionomers , 2014 .

[8]  H. Ardebili,et al.  High performance solid polymer electrolyte with graphene oxide nanosheets , 2014 .

[9]  Michio Koinuma,et al.  Proton conductivities of graphene oxide nanosheets: single, multilayer, and modified nanosheets. , 2014, Angewandte Chemie.

[10]  Wei Gao,et al.  Ozonated graphene oxide film as a proton-exchange membrane. , 2014, Angewandte Chemie.

[11]  K. Ghandi A Review of Ionic Liquids, Their Limits and Applications , 2014 .

[12]  Xin Cai,et al.  Flexible planar/fiber-architectured supercapacitors for wearable energy storage , 2014 .

[13]  Keun-Ho Choi,et al.  Thin, Deformable, and Safety‐Reinforced Plastic Crystal Polymer Electrolytes for High‐Performance Flexible Lithium‐Ion Batteries , 2014 .

[14]  M. Dresselhaus,et al.  Ultrahigh humidity sensitivity of graphene oxide , 2013, Scientific Reports.

[15]  Tengfei Zhang,et al.  A High‐Performance Graphene Oxide‐Doped Ion Gel as Gel Polymer Electrolyte for All‐Solid‐State Supercapacitor Applications , 2013 .

[16]  Yan-Jie Wang,et al.  Alkaline polymer electrolyte membranes for fuel cell applications. , 2013, Chemical Society reviews.

[17]  Takeshi Matsui,et al.  Graphene oxide nanosheet with high proton conductivity. , 2013, Journal of the American Chemical Society.

[18]  D. Basko,et al.  Raman spectroscopy as a versatile tool for studying the properties of graphene. , 2013, Nature nanotechnology.

[19]  L. Ricardez‐Sandoval,et al.  Pyrrolic-structure enriched nitrogen doped graphene for highly efficient next generation supercapacitors , 2013 .

[20]  M. Otyepka,et al.  Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. , 2012, Chemical reviews.

[21]  Y. Matsumoto,et al.  Photochemical Engineering of Graphene Oxide Nanosheets , 2012 .

[22]  Yong Liu,et al.  Functionalization of Graphene Oxide with Polyhedral Oligomeric Silsesquioxane (POSS) for Multifunctional Applications. , 2012, The journal of physical chemistry letters.

[23]  K. Scott,et al.  Freestanding sulfonated graphene oxide paper: a new polymer electrolyte for polymer electrolyte fuel cells. , 2012, Chemical communications.

[24]  Yongsheng Chen,et al.  Rapid and effective functionalization of graphene oxide by ionic liquid. , 2012, Journal of nanoscience and nanotechnology.

[25]  I. Grigorieva,et al.  Unimpeded Permeation of Water Through Helium-Leak–Tight Graphene-Based Membranes , 2011, Science.

[26]  K. Seethalakshmi,et al.  FT-IR SPECTRAL ANALYSIS OF IMIDAZOLIUM CHLORIDE - , 2012 .

[27]  K. Scott,et al.  A Graphite Oxide Paper Polymer Electrolyte for Direct Methanol Fuel Cells , 2011 .

[28]  Yu Jun,et al.  Functionalized Graphene Oxide Nanocomposite Membrane for Low Humidity and High Temperature Proton Exchange Membrane Fuel Cells , 2011 .

[29]  M. Guiver,et al.  Guanidinium-Functionalized Anion Exchange Polymer Electrolytes via Activated Fluorophenyl-Amine Reaction , 2011 .

[30]  Xueliang Sun,et al.  Nitrogen doping effects on the structure of graphene , 2011 .

[31]  K. Cooper Characterizing Through-Plane and In-Plane Ionic Conductivity of Polymer Electrolyte Membranes , 2011 .

[32]  Yi Cui,et al.  Solution-processed graphene/MnO2 nanostructured textiles for high-performance electrochemical capacitors. , 2011, Nano letters.

[33]  S. Huh,et al.  Thermal Reduction of Graphene Oxide , 2011 .

[34]  Yiying Wu,et al.  Preparation, characterization, and electrocatalytic performance of graphene-methylene blue thin films , 2011 .

[35]  Wei Li,et al.  Synthesis and characterization of novel anion exchange membranes based on imidazolium-type ionic liquid for alkaline fuel cells , 2010 .

[36]  C. N. Lau,et al.  Spectroscopy of covalently functionalized graphene. , 2010, Nano letters.

[37]  Hongkun He,et al.  General Approach to Individually Dispersed, Highly Soluble, and Conductive Graphene Nanosheets Functionalized by Nitrene Chemistry , 2010 .

[38]  W. Lu,et al.  Improved synthesis of graphene oxide. , 2010, ACS nano.

[39]  Kinga Haubner,et al.  The route to functional graphene oxide. , 2010, Chemphyschem : a European journal of chemical physics and physical chemistry.

[40]  R. Ruoff,et al.  Review of Best Practice Methods for Determining an Electrode Material's Performance for Ultracapacitors , 2010, 1005.0805.

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

[42]  C. Iojoiu,et al.  Composite polymer electrolytes for electrochemical devices , 2010 .

[43]  Sun Tai Kim,et al.  Metal–Air Batteries with High Energy Density: Li–Air versus Zn–Air , 2010 .

[44]  Bruno Scrosati,et al.  Ionic-liquid materials for the electrochemical challenges of the future. , 2009, Nature materials.

[45]  Huafeng Yang,et al.  Covalent functionalization of polydisperse chemically-converted graphene sheets with amine-terminated ionic liquid. , 2009, Chemical communications.

[46]  SonBinh T. Nguyen,et al.  Aqueous Suspension and Characterization of Chemically Modified Graphene Sheets , 2008 .

[47]  T. Navessin,et al.  Investigation of the through-plane impedance technique for evaluation of anisotropy of proton conducting polymer membranes , 2008 .

[48]  P. Knauth,et al.  Proton-Conducting Nanocomposites and Hybrid Polymers , 2008 .

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

[50]  J. Varcoe Investigations of the ex situ ionic conductivities at 30 degrees C of metal-cation-free quaternary ammonium alkaline anion-exchange membranes in static atmospheres of different relative humidities. , 2007, Physical chemistry chemical physics : PCCP.

[51]  Alexandra Buchsteiner,et al.  Water dynamics in graphite oxide investigated with neutron scattering. , 2006, The journal of physical chemistry. B.

[52]  Ado Jorio,et al.  General equation for the determination of the crystallite size La of nanographite by Raman spectroscopy , 2006 .

[53]  Hui Ye,et al.  Novel zinc ion conducting polymer gel electrolytes based on ionic liquids , 2005 .

[54]  Jean-François Fauvarque,et al.  Electrochemical properties of an alkaline solid polymer electrolyte based on P(ECH-co-EO) , 2000 .

[55]  M. Karjalainen,et al.  New Polymer Electrolyte Membranes for Low Temperature Fuel Cells , 1999 .

[56]  C. Makaroff,et al.  Alkaline opening of imidazole ring of 7-methylguanosine. 2. Further studies on reaction mechanisms and products. , 1982, Chemico-biological interactions.

[57]  F. Tuinstra,et al.  Raman Spectrum of Graphite , 1970 .

[58]  W. S. Hummers,et al.  Preparation of Graphitic Oxide , 1958 .