Tuning the structure of in-situ synthesized few layer graphene/carbon composites into nanoporous vertically aligned graphene electrodes with high volumetric capacitance

Abstract Few layer graphene/carbon (FLG/C) composites are prepared directly via the rapid and simple exfoliation of expanded graphite in the presence of carbon based natural precursors (i.e. protein, polysaccharide) in water, followed by carbonization process. Several parameters such as nature of C-precursor, FLG/C ratio and carbonization conditions (gas, temperature) are modified in order to optimize the morphology, composition and porosity of FLG/C and thereby investigate their impact on gravimetric and volumetric capacitance, their stability and contribution of pseudocapacitance (Ps) vs. Double-layer capacitance (DL). Few composites exhibit extremely high capacitance considering their low BET-surface area ranging in 130–260 m2/g. The highest gravimetric and volumetric capacitance of 322 F/g and 467 F/cm3 respectively (0.5 A/g); and energy/power performance is reached for FLG/C:1/2, synthesized from graphite-bovine serum albumin (BSA). Despite relatively high theoretical pseudocapacitance contribution of 69% (1.1 V), this sample shows also high capacity retention at high current density and elevated energy -to- power densities. The overall great capacity performance is attributed to the high electrochemical surface area from combined structural features: ultramicroporosity, FLG alignment with high accessibility of FLG edges and elevated packing density. The transport limitation enhances however at higher scan rate (>100 mV/s).

[1]  Yang Bai,et al.  Supercapacitors with high capacitance based on reduced graphene oxide/carbon nanotubes/NiO composite electrodes , 2014 .

[2]  Tim Lincoln,et al.  Chemical communications , 1992, Nature.

[3]  B. Jang,et al.  Graphene-based supercapacitor with an ultrahigh energy density. , 2010, Nano letters.

[4]  J. Silvestre-Albero,et al.  Low-Pressure Hysteresis in Adsorption: An Artifact? , 2012 .

[5]  I. Ial,et al.  Nature Communications , 2010, Nature Cell Biology.

[6]  Chi-Chang Hu,et al.  New Approach for High-Voltage Electrical Double-Layer Capacitors Using Vertical Graphene Nanowalls with and without Nitrogen Doping. , 2016, Nano letters.

[7]  E. Yeager,et al.  Differential Capacitance Study of Stress‐Annealed Pyrolytic Graphite Electrodes , 1971 .

[8]  F. Béguin,et al.  Electrochemical Capacitors Based on Carbon Electrodes in Aqueous Electrolytes , 2015 .

[9]  R. Lobo Microporous and Mesoporous Materials , 2014 .

[10]  P. Aubert,et al.  Polypyrrole-modified graphene sheet nanocomposites as new efficient materials for supercapacitors , 2016 .

[11]  H. Häkkinen,et al.  The Journal of Physical Chemistry C Virtual Special Issue on Metal Clusters, Nanoparticles, and the Physical Chemistry of Catalysis , 2021 .

[12]  Ki Chul Park,et al.  Edge-enriched, porous carbon-based, high energy density supercapacitors for hybrid electric vehicles. , 2012, ChemSusChem.

[13]  Yunhui Huang,et al.  Tuning and understanding the supercapacitance of heteroatom-doped graphene , 2015 .

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

[15]  Zhimin Xie,et al.  Preparation and properties of aligned graphene composites , 2015 .

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

[17]  C. Pham‐Huu,et al.  Biosourced Foam‐Like Activated Carbon Materials as High‐Performance Supercapacitors , 2018 .

[18]  I. S. Turan,et al.  RSC Advances , 2015 .

[19]  L. Qu,et al.  Vertically Aligned Graphene Sheets Membrane for Highly Efficient Solar Thermal Generation of Clean Water. , 2017, ACS nano.

[20]  I. Janowska Evaporation-induced self-assembling of few-layer graphene into a fractal-like conductive macro-network with a reduction of percolation threshold. , 2015, Physical chemistry chemical physics : PCCP.

[21]  A. Cooper,et al.  Controlling electric double-layer capacitance and pseudocapacitance in heteroatom-doped carbons derived from hypercrosslinked microporous polymers , 2018 .

[22]  L. Christophorou Science , 2018, Emerging Dynamics: Science, Energy, Society and Values.

[23]  R. Williams,et al.  Journal of American Chemical Society , 1979 .

[24]  J. Xie,et al.  Preparation of High-surface-area Carbon Nanoparticle/Graphene Composites , 2012 .

[25]  A. Toland,et al.  Carbon , 2018, Field to Palette.

[26]  C. Pham‐Huu,et al.  Colloid Approach to the Sustainable Top-Down Synthesis of Layered Materials , 2017, ACS omega.

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

[28]  Yongsheng Chen,et al.  Controlling the effective surface area and pore size distribution of sp2 carbon materials and their impact on the capacitance performance of these materials. , 2013, Journal of the American Chemical Society.

[29]  R. Rosenfeld Nature , 2009, Otolaryngology--head and neck surgery : official journal of American Academy of Otolaryngology-Head and Neck Surgery.

[30]  C. Clarkson,et al.  On the use and abuse of N2 physisorption for the characterization of the pore structure of shales , 2016 .

[31]  S. Shekhar,et al.  Ultrahigh performance supercapacitor from lacey reduced graphene oxide nanoribbons. , 2015, ACS applied materials & interfaces.

[32]  Li Zhang,et al.  Preparation of Highly Conductive Graphene Hydrogels for Fabricating Supercapacitors with High Rate Capability , 2011 .

[33]  P. Ajayan,et al.  Ultrathin planar graphene supercapacitors. , 2011, Nano letters.

[34]  Bin Wang,et al.  Supercapacitor Electrodes with Remarkable Specific Capacitance Converted from Hybrid Graphene Oxide/NaCl/Urea Films. , 2017, ACS applied materials & interfaces.

[35]  F. Kapteijn,et al.  Adsorptive characterization of porous solids: Error analysis guides the way , 2014 .

[36]  G. Shi,et al.  Three-dimensional graphene architectures. , 2012, Nanoscale.

[37]  Y. X. Wang,et al.  Nuclear Instruments and Methods in Physics Research Section B : Beam Interactions with Materials and Atoms , 2018 .

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

[39]  Yufeng Zhao,et al.  Ultrahigh volumetric capacitance and cyclic stability of fluorine and nitrogen co-doped carbon microspheres , 2015, Nature Communications.

[40]  X. Qin,et al.  Sugar-derived carbon/graphene composite materials as electrodes for supercapacitors , 2014 .

[41]  Keita Nomura,et al.  4.4 V supercapacitors based on super-stable mesoporous carbon sheet made of edge-free graphene walls , 2019, Energy & Environmental Science.

[42]  Wei Lv,et al.  Towards ultrahigh volumetric capacitance: graphene derived highly dense but porous carbons for supercapacitors , 2013, Scientific Reports.

[43]  Yeon Jun Choi,et al.  Scalable fabrication of micron-scale graphene nanomeshes for high-performance supercapacitor applications , 2016 .

[44]  Ashutosh Tiwari,et al.  Advanced Energy Materials , 2014 .

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

[46]  N. Krstajić,et al.  Reply to “note on a method to interrelate inner and outer electrode areas” by H. Vogt , 1994 .

[47]  이현주 Q. , 2005 .

[48]  Boris E. Burakov,et al.  Advanced Materials , 2019, Springer Proceedings in Physics.

[49]  A. D. Todd,et al.  Harnessing the chemistry of graphene oxide. , 2014, Chemical Society reviews.

[50]  A. Hirata,et al.  An ultrahigh volumetric capacitance of squeezable three-dimensional bicontinuous nanoporous graphene. , 2016, Nanoscale.

[51]  G. Cheng,et al.  Fabricating vertically aligned ultrathin graphene nanosheets without any catalyst using rf sputtering deposition , 2013 .

[52]  Bo You,et al.  Three dimensional N-doped graphene-CNT networks for supercapacitor. , 2013, Chemical communications.

[53]  Mykola Seredych,et al.  Combined Effect of Nitrogen‐ and Oxygen‐Containing Functional Groups of Microporous Activated Carbon on its Electrochemical Performance in Supercapacitors , 2009 .

[54]  Matthew J. Rosseinsky,et al.  Advanced Functional Materials , 2015, Materials Science Forum.

[55]  Chi-Chang Hu,et al.  Differentiate the pseudocapacitance and double-layer capacitance contributions for nitrogen-doped reduced graphene oxide in acidic and alkaline electrolytes , 2013 .

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

[57]  Yury Gogotsi,et al.  Thickness-independent capacitance of vertically aligned liquid-crystalline MXenes , 2018, Nature.

[58]  M. Itagaki,et al.  Achieving 100% Utilization of Reduced Graphene Oxide by Layer-by-Layer Assembly: Insight into the Capacitance of Chemically Derived Graphene in a Monolayer State , 2014 .

[59]  Jian Li,et al.  A doped activated carbon prepared from polyaniline for high performance supercapacitors , 2010 .

[60]  Bin Wang,et al.  Freeze-Casting Produces a Graphene Oxide Aerogel with a Radial and Centrosymmetric Structure. , 2018, ACS nano.

[61]  Y. Kim,et al.  Important roles of graphene edges in carbon-based energy storage devices , 2013 .

[62]  Ten-Chin Wen,et al.  Electrochemical and capacitive properties of polyaniline-implanted porous carbon electrode for supercapacitors , 2003 .

[63]  Alexander J. Pak,et al.  Impact of Graphene Edges on Enhancing the Performance of Electrochemical Double Layer Capacitors , 2014 .

[64]  G. Wasserburg The chemical record , 1989 .

[65]  Sergey N. Pronkin,et al.  Edges fractal approach in graphene – Defects density gain , 2017, 2301.03449.

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

[67]  Y. Yoon,et al.  Vertical alignments of graphene sheets spatially and densely piled for fast ion diffusion in compact supercapacitors. , 2014, ACS nano.

[68]  D. L. Mafra,et al.  Controlled porous structures of graphene aerogels and their effect on supercapacitor performance. , 2015, Nanoscale.

[69]  Zhongfan Liu,et al.  The edge- and basal-plane-specific electrochemistry of a single-layer graphene sheet , 2013, Scientific Reports.

[70]  P. Chu,et al.  Direct anodic exfoliation of graphite onto high-density aligned graphene for large capacity supercapacitors , 2017 .

[71]  Jianjun Niu,et al.  Requirements for performance characterization of C double-layer supercapacitors: Applications to a high specific-area C-cloth material , 2006 .

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

[73]  Martin Pumera,et al.  Electrochemistry of graphene: new horizons for sensing and energy storage. , 2009, Chemical record.

[74]  Chris D. Geddes,et al.  Physical Chemistry Chemical Physics , 2013 .

[75]  Junpeng Liu,et al.  High-performance supercapacitor electrodes based on highly corrugated graphene sheets , 2012 .

[76]  H. Exner,et al.  Geographical variation in morphology of Chaetosiphella stipae stipae Hille Ris Lambers, 1947 (Hemiptera: Aphididae: Chaitophorinae) , 2017, Scientific Reports.