Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors.

A novel type of highly flexible and all-solid-state supercapacitor that uses cellulose nanofibril (CNF)/reduced graphene oxide (RGO)/carbon nanotube (CNT) hybrid aerogels as electrodes and H2SO4/poly(vinyl alcohol) (PVA) gel as the electrolyte was developed and is reported here. These flexible solid-state supercapacitors were fabricated without any binders, current collectors, or electroactive additives. Because of the porous structure of the CNF/RGO/CNT aerogel electrodes and the excellent electrolyte absorption properties of the CNFs present in the aerogel electrodes, the resulting flexible supercapacitors exhibited a high specific capacitance (i.e., 252 F g(-1) at a discharge current density of 0.5 A g(-1)) and a remarkable cycle stability (i.e., more than 99.5% of the capacitance was retained after 1000 charge-discharge cycles at a current density of 1 A g(-1)). Furthermore, the supercapacitors also showed extremely high areal capacitance, areal power density, and energy density (i.e., 216 mF cm(-2), 9.5 mW cm(-2), and 28.4 μWh cm(-2), respectively). In light of its excellent electrical performance, low cost, ease of large-scale manufacturing, and environmental friendliness, the CNF/RGO/CNT aerogel electrodes may have a promising application in the development of flexible energy-storage devices.

[1]  L. Mattoso,et al.  Cellulose micro/nanofibres from Eucalyptus kraft pulp: preparation and properties. , 2012, Carbohydrate polymers.

[2]  Franklin Kim,et al.  Graphene oxide sheets at interfaces. , 2010, Journal of the American Chemical Society.

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

[4]  Chao Gao,et al.  Multifunctional, Ultra‐Flyweight, Synergistically Assembled Carbon Aerogels , 2013, Advanced materials.

[5]  Fei Liu,et al.  Folded Structured Graphene Paper for High Performance Electrode Materials , 2012, Advanced materials.

[6]  H. Sehaqui,et al.  High-porosity aerogels of high specific surface area prepared from nanofibrillated cellulose (NFC) , 2011 .

[7]  Chang Liu,et al.  Advanced Materials for Energy Storage , 2010, Advanced materials.

[8]  Z. Cai,et al.  Polyvinyl alcohol-cellulose nanofibrils-graphene oxide hybrid organic aerogels. , 2013, ACS applied materials & interfaces.

[9]  Jian Li,et al.  Ultralight and highly flexible aerogels with long cellulose I nanofibers , 2011 .

[10]  徐朝和,et al.  Graphene-based electrodes for electrochemical energy storage , 2013 .

[11]  Dieter Klemm,et al.  Nanocelluloses: A New Family of Nature-Based Materials , 2011 .

[12]  G. Shi,et al.  Graphene based new energy materials , 2011 .

[13]  R. Chandrasekaran,et al.  Preparation and electrochemical performance of activated carbon thin films with polyethylene oxide-salt addition for electrochemical capacitor applications , 2008 .

[14]  Zhongwei Chen,et al.  Ultrathin, transparent, and flexible graphene films for supercapacitor application , 2010 .

[15]  Xiaodong Li,et al.  Towards Textile Energy Storage from Cotton T‐Shirts , 2012, Advanced materials.

[16]  Xinliang Feng,et al.  Porous Graphene Materials for Advanced Electrochemical Energy Storage and Conversion Devices , 2014, Advanced materials.

[17]  Yunqi Liu,et al.  One-pot self-assembled three-dimensional TiO2-graphene hydrogel with improved adsorption capacities and photocatalytic and electrochemical activities. , 2013, ACS applied materials & interfaces.

[18]  Yunqi Liu,et al.  Freestanding graphene paper supported three-dimensional porous graphene-polyaniline nanocomposite synthesized by inkjet printing and in flexible all-solid-state supercapacitor. , 2014, ACS applied materials & interfaces.

[19]  Z. Cai,et al.  Polyvinyl alcohol (PVA)–cellulose nanofibril (CNF)–multiwalled carbon nanotube (MWCNT) hybrid organic aerogels with superior mechanical properties , 2013 .

[20]  Xiaogang Han,et al.  Natural cellulose fiber as substrate for supercapacitor. , 2013, ACS nano.

[21]  G. Shi,et al.  Graphene Hydrogels Deposited in Nickel Foams for High‐Rate Electrochemical Capacitors , 2012, Advanced materials.

[22]  L. Nyholm,et al.  Toward Flexible Polymer and Paper‐Based Energy Storage Devices , 2011, Advanced materials.

[23]  Zhanhu Guo,et al.  Electropolymerized Polyaniline Nanocomposites from Multi-Walled Carbon Nanotubes with Tuned Surface Functionalities for Electrochemical Energy Storage , 2013 .

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

[25]  Bei Wang,et al.  Synthesis and characterisation of hydrophilic and organophilic graphene nanosheets , 2009 .

[26]  Feng Li,et al.  Graphene–Cellulose Paper Flexible Supercapacitors , 2011 .

[27]  L. Dao,et al.  New Class of Carbon‐Nanotube Aerogel Electrodes for Electrochemical Power Sources , 2008 .

[28]  R. Ruoff,et al.  Graphene and Graphene Oxide: Synthesis, Properties, and Applications , 2010, Advanced materials.

[29]  J. Youngblood,et al.  Cellulose Nanomaterials Review: Structure, Properties and Nanocomposites , 2011 .

[30]  Jun Song Chen,et al.  Nitrogen-containing microporous carbon nanospheres with improved capacitive properties , 2011 .

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

[32]  Lili Zhang,et al.  Graphene-based materials as supercapacitor electrodes , 2010 .

[33]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[34]  N. Renganathan,et al.  Acrylamide based proton conducting polymer gel electrolyte for electric double layer capacitors , 2008 .

[35]  Kai Zhang,et al.  Graphene/Polyaniline Nanofiber Composites as Supercapacitor Electrodes , 2010 .

[36]  Yi Cui,et al.  Aqueous supercapacitors on conductive cotton , 2010 .

[37]  D. Klemm,et al.  Cellulose: fascinating biopolymer and sustainable raw material. , 2005, Angewandte Chemie.

[38]  Luzhuo Chen,et al.  Highly flexible and all-solid-state paperlike polymer supercapacitors. , 2010, Nano letters.

[39]  Guang Yang,et al.  Flexible Supercapacitors Based on Bacterial Cellulose Paper Electrodes , 2014 .

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

[41]  Yonggang Huang,et al.  Materials and Mechanics for Stretchable Electronics , 2010, Science.

[42]  D. Gokhale,et al.  Combined strategy for the dispersion/dissolution of single walled carbon nanotubes and cellulose in water , 2011 .

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

[44]  Changsheng Liu,et al.  Flexible pillared graphene-paper electrodes for high-performance electrochemical supercapacitors. , 2012, Small.

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

[46]  Hiroyuki Nishide,et al.  Toward Flexible Batteries , 2008, Science.

[47]  A. Isogai,et al.  Entire surface oxidation of various cellulose microfibrils by TEMPO-mediated oxidation. , 2010, Biomacromolecules.

[48]  Guohua Chen,et al.  One-step in situball milling synthesis of polymer-functionalized graphene nanocomposites , 2011 .

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

[50]  Sanjun Fan,et al.  Three-dimensional hierarchically porous all-carbon foams for supercapacitor. , 2014, ACS applied materials & interfaces.

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

[52]  Martin Pumera,et al.  Graphene-based nanomaterials for energy storage , 2011 .

[53]  Khalil Amine,et al.  Chemically active reduced graphene oxide with tunable C/O ratios. , 2011, ACS nano.

[54]  Feijun Wang,et al.  Cellulose nanofiber–graphene all solid-state flexible supercapacitors , 2013 .

[55]  Jiayan Luo,et al.  Graphene oxide as surfactant sheets , 2010 .

[56]  Z. Cai,et al.  Green synthesis of polyvinyl alcohol (PVA)–cellulose nanofibril (CNF) hybrid aerogels and their use as superabsorbents , 2014 .

[57]  Yunqi Liu,et al.  Facile Synthesis of 3D MnO2–Graphene and Carbon Nanotube–Graphene Composite Networks for High‐Performance, Flexible, All‐Solid‐State Asymmetric Supercapacitors , 2014 .

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

[59]  Bo-Yeong Kim,et al.  All-solid-state flexible supercapacitors fabricated with bacterial nanocellulose papers, carbon nanotubes, and triblock-copolymer ion gels. , 2012, ACS nano.

[60]  Bing M. Fung,et al.  Organic Aerogels with Very High Impact Strength , 2001 .

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

[62]  Xu Xiao,et al.  Paper-based supercapacitors for self-powered nanosystems. , 2012, Angewandte Chemie.

[63]  Xingwei Li,et al.  High-performance asymmetric supercapacitor based on nanoarchitectured polyaniline/graphene/carbon nanotube and activated graphene electrodes. , 2013, ACS applied materials & interfaces.