Continuously hierarchical nanoporous graphene film for flexible solid-state supercapacitors with excellent performance

Abstract Continuously hierarchical nanoporous graphene (hnp-G) films are synthesized by a combination of low-temperature CVD growth of hydrogenated graphite (HG) coating on nanoporous copper (NPC) and rapid catalytic pyrolysis of HG at high temperature. Low-temperature growth of HG coating on NPC can obviously delay the coarsening evolution of NPC at high temperature, providing the precondition to obtain hnp-G with small pore size (1–150 nm) by catalytic pyrolysis at high temperature. The high specific surface area (1160 m 2 /g) of hnp-G are mainly originated from the external surface (954.7 m 2 /g), resulting in fully accessible channels for ion transport. More importantly, the continuously 3D hierarchical nanoporous structure and fully wettability of the hnp-G with gelled electrolyte not only effectively prevent the restacking of graphene even under dramatic squeezing but also guarantee the continuous and short electron/ion diffusion pathway in the whole electrodes, resulting in ultrahigh specific capacitance (38.2 F/cm 3 based on the device) and excellent rate performance. The symmetric SC offers ultrahigh energy density (2.65 mW h/cm 3 ) and power density (20.8 W/cm 3 ) and exhibits almost identical performance at various curvatures and excellent lifetime (94% retention after 10,000 cycles), suggesting its wide application potential in powering wearable/miniaturized electronics.

[1]  Rudolf Holze,et al.  Supercapacitors Based on Flexible Substrates: An Overview , 2014 .

[2]  Shuang Yuan,et al.  Advances and challenges for flexible energy storage and conversion devices and systems , 2014 .

[3]  Dingshan Yu,et al.  Controlled Functionalization of Carbonaceous Fibers for Asymmetric Solid‐State Micro‐Supercapacitors with High Volumetric Energy Density , 2014, Advanced materials.

[4]  G. Shi,et al.  Self-assembled graphene hydrogel via a one-step hydrothermal process. , 2010, ACS nano.

[5]  Lele Peng,et al.  Two dimensional nanomaterials for flexible supercapacitors. , 2014, Chemical Society reviews.

[6]  T. Fujita,et al.  Bicontinuous Nanoporous N‐doped Graphene for the Oxygen Reduction Reaction , 2014, Advanced materials.

[7]  John Robertson,et al.  Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon , 2001 .

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

[9]  B. Liu,et al.  Flexible Energy‐Storage Devices: Design Consideration and Recent Progress , 2014, Advanced materials.

[10]  W. Mai,et al.  Significantly enhanced robustness and electrochemical performance of flexible carbon nanotube-based supercapacitors by electrodepositing polypyrrole , 2015 .

[11]  Majid Beidaghi,et al.  Capacitive energy storage in micro-scale devices: recent advances in design and fabrication of micro-supercapacitors , 2014 .

[12]  Li-Jun Wan,et al.  Hydrothermal reduction of three-dimensional graphene oxide for binder-free flexible supercapacitors , 2014 .

[13]  Nobuo Tanaka,et al.  Atomic origins of the high catalytic activity of nanoporous gold. , 2012, Nature materials.

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

[15]  Junling Xu,et al.  Low-temperature Ni particle-templated chemical vapor deposition growth of curved graphene for supercapacitor applications , 2015 .

[16]  Zhenxing Zhang,et al.  Freestanding three-dimensional graphene/MnO2 composite networks as ultralight and flexible supercapacitor electrodes. , 2013, ACS nano.

[17]  Wei Lv,et al.  Towards superior volumetric performance: design and preparation of novel carbon materials for energy storage , 2015 .

[18]  Wenjie Mai,et al.  Flexible solid-state electrochemical supercapacitors , 2014 .

[19]  Klaus Müllen,et al.  Graphene-based in-plane micro-supercapacitors with high power and energy densities , 2013, Nature Communications.

[20]  A. Alú,et al.  Errautm: Intrinsic optical properties and enhanced plasmonic response of epitaxial silver (Advanced Materials (2014) 26 (6106-6110)) , 2014 .

[21]  John R. Miller,et al.  Graphene Double-Layer Capacitor with ac Line-Filtering Performance , 2010, Science.

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

[23]  B. Scrosati,et al.  The role of graphene for electrochemical energy storage. , 2015, Nature materials.

[24]  J. Robertson,et al.  Defect and disorder reduction by annealing in hydrogenated tetrahedral amorphous carbon , 2000 .

[25]  Robertson,et al.  Electronic and atomic structure of amorphous carbon. , 1987, Physical review. B, Condensed matter.

[26]  Chi Cheng,et al.  Liquid-Mediated Dense Integration of Graphene Materials for Compact Capacitive Energy Storage , 2013, Science.

[27]  Zhijun Qiao,et al.  Free-standing porous carbon nanofiber/ultrathin graphite hybrid for flexible solid-state supercapacitors. , 2015, ACS nano.

[28]  Chunxiang Lu,et al.  Hierarchical Porous Graphene Carbon-Based Supercapacitors , 2015 .

[29]  Baohua Li,et al.  Co-electro-deposition of the MnO2–PEDOT:PSS nanostructured composite for high areal mass, flexible asymmetric supercapacitor devices , 2013 .

[30]  Taeyoung Kim,et al.  Activated graphene-based carbons as supercapacitor electrodes with macro- and mesopores. , 2013, ACS nano.

[31]  Klaus Müllen,et al.  Ultrathin Printable Graphene Supercapacitors with AC Line‐Filtering Performance , 2015, Advanced materials.

[32]  M. El‐Kady,et al.  Scalable fabrication of high-power graphene micro-supercapacitors for flexible and on-chip energy storage , 2013, Nature Communications.

[33]  Cheng Yang,et al.  Scalable fabrication of MnO2 nanostructure deposited on free-standing Ni nanocone arrays for ultrathin, flexible, high-performance micro-supercapacitor , 2014 .

[34]  Huiling Yang,et al.  Flexible Asymmetric Micro‐Supercapacitors Based on Bi2O3 and MnO2 Nanoflowers: Larger Areal Mass Promises Higher Energy Density , 2015 .

[35]  G. Gary Wang,et al.  Flexible solid-state supercapacitors: design, fabrication and applications , 2014 .

[36]  Takeshi Fujita,et al.  High-quality three-dimensional nanoporous graphene. , 2014, Angewandte Chemie.

[37]  T. Fujita,et al.  High catalytic activity of nitrogen and sulfur co-doped nanoporous graphene in the hydrogen evolution reaction. , 2015, Angewandte Chemie.

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

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

[40]  K. M. Tripathi,et al.  Recent progress in micro-scale energy storage devices and future aspects , 2015 .

[41]  Hui‐Ming Cheng,et al.  Three-dimensional flexible and conductive interconnected graphene networks grown by chemical vapour deposition. , 2011, Nature materials.

[42]  Qinghua Zhang,et al.  Free-standing three-dimensional graphene and polyaniline nanowire arrays hybrid foams for high-performance flexible and lightweight supercapacitors , 2014 .

[43]  Wei Chen,et al.  3D graphene nanomaterials for binder-free supercapacitors: scientific design for enhanced performance. , 2015, Nanoscale.

[44]  Teng Zhai,et al.  Solid‐State Supercapacitor Based on Activated Carbon Cloths Exhibits Excellent Rate Capability , 2014, Advanced materials.

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

[46]  Min Wei,et al.  Hierarchical NiMn Layered Double Hydroxide/Carbon Nanotubes Architecture with Superb Energy Density for Flexible Supercapacitors , 2014 .

[47]  Tae Hoon Lee,et al.  Carbon nanotube-bridged graphene 3D building blocks for ultrafast compact supercapacitors. , 2015, ACS nano.