Electrochemical charge storage in hierarchical carbon manifolds

Abstract The use of hierarchical assemblies constituted from macroporous structures (e.g., reticulated vitreous carbon, RVC) where the internal pore area is covered with closely spaced nanostructures (e.g., carbon nanotubes, CNT) is proposed for substantially enhancing the energy density of electrochemical capacitors, while maintaining large charge/discharge rates. While the macroscale pores enable storage of substantial electrolyte volumes that would contribute through redox reactions to the energy density, the closely spaced nanostructures provide a large geometric area and capacitance in addition to enabling rate independent Faradaic charge storage via thin layer electrochemistry (TLE). A fifty fold increase in the double layer capacitance, in addition to increased Faradaic charge density – with potential for orders of magnitude improvement, was observed for the RVC-CNT electrodes, in comparison to the bare RVC foam electrode. It was seen that the hierarchical assembly enables the contribution from ∼94% of the net volume of the wetted RVC-CNT electrode for active Faradaic charge storage.

[1]  A. Manthiram.  Correction to “Materials Challenges and Opportunities of Lithium Ion Batteries” , 2011 .

[2]  Wendy G. Pell,et al.  Voltammetry at a de Levie brush electrode as a model for electrochemical supercapacitor behaviour , 2001 .

[3]  Hema Vijwani,et al.  Hierarchical hybrid carbon nano-structures as robust and reusable adsorbents: Kinetic studies with model dye compound , 2015 .

[4]  Kristopher R. Ward,et al.  Thin-layer vs. semi-infinite diffusion in cylindrical pores: A basis for delineating Fickian transport to identify nano-confinement effects in voltammetry , 2013 .

[5]  J. Weidner,et al.  Ohmic distortion of reversible voltammograms in thin-layer cells , 1988 .

[6]  M. Hoefer,et al.  Determination and enhancement of the capacitance contributions in carbon nanotube based electrode systems , 2009 .

[7]  J. Goodenough.  Challenges for Rechargeable Li Batteries , 2010 .

[8]  S. T. Senthilkumar,et al.  Electric double layer capacitor and its improved specific capacitance using redox additive electrolyte , 2013 .

[9]  Frank C. Walsh,et al.  Reticulated vitreous carbon as an electrode material , 2004 .

[10]  Kristopher R. Ward,et al.  Understanding Voltammetry , 2018 .

[11]  John R Miller,et al.  Valuing Reversible Energy Storage , 2012, Science.

[12]  E. Frąckowiak,et al.  Electrochemistry serving people and nature: high-energy ecocapacitors based on redox-active electrolytes. , 2012, ChemSusChem.

[13]  G. G. Stokes.  "J." , 1890, The New Yale Book of Quotations.

[14]  B. Conway.  Transition from “Supercapacitor” to “Battery” Behavior in Electrochemical Energy Storage , 1991 .

[15]  Bruce Dunn,et al.  High-rate electrochemical energy storage through Li+ intercalation pseudocapacitance. , 2013, Nature materials.

[16]  F. Béguin,et al.  Unusual energy enhancement in carbon-based electrochemical capacitors , 2012 .

[17]  Joseph Wang,et al.  RETICULATED VITREOUS CARBON. A NEW VERSATILE ELECTRODE MATERIAL , 1982 .

[18]  B. McDuffie,et al.  Diffusion coefficients of ferri- and ferrocyanide ions in aqueous media, using twin-electrode thin-layer electrochemistry , 1970 .

[19]  Mingming Chen,et al.  Hierarchical porous carbon derived from sulfonated pitch for electrical double layer capacitors , 2014 .

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

[21]  R. Compton,et al.  Mass transport to and within porous electrodes. Linear sweep voltammetry and the effects of pore size: The prediction of double peaks for a single electrode process , 2012, Russian Journal of Electrochemistry.

[22]  J. Nichols,et al.  Artificial introduction of defects into vertically aligned multiwalled carbon nanotube ensembles: Application to electrochemical sensors , 2007 .

[23]  R. Compton,et al.  Voltammetry at porous electrodes: A theoretical study , 2014, 1407.1722.

[24]  S. Mukhopadhyay,et al.  Specific surface area of hierarchical graphitic substrates suitable for multi-functional applications , 2012 .

[25]  B. Dunn,et al.  Pseudocapacitive oxide materials for high-rate electrochemical energy storage , 2014 .

[26]  John R. Miller,et al.  Electrochemical Capacitors: Challenges and Opportunities for Real-World Applications , 2008 .

[27]  E. Frąckowiak,et al.  Electrochemical capacitors as attractive power sources , 2014 .

[28]  Hyun-Wook Lee,et al.  A pomegranate-inspired nanoscale design for large-volume-change lithium battery anodes. , 2014, Nature nanotechnology.

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

[30]  Hang Shi,et al.  Studies of activated carbons used in double-layer capacitors , 1998 .

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

[32]  S. Mukhopadhyay,et al.  Hierarchical nanostructures by nanotube grafting on porous cellular surfaces , 2009 .

[33]  Doron Aurbach,et al.  Carbon Electrodes for Double‐Layer Capacitors I. Relations Between Ion and Pore Dimensions , 2000 .

[34]  R. Menéndez,et al.  Mechanisms of Energy Storage in Carbon-Based Supercapacitors Modified with a Quinoid Redox-Active Electrolyte , 2011 .

[35]  R. Narayanan,et al.  High Rate Capacity through Redox Electrolytes Confined in Macroporous Electrodes , 2015 .

[36]  Artur Braun,et al.  Exponential growth of electrochemical double layer capacitance in glassy carbon during thermal oxidation , 2003 .

[37]  P. Bandaru,et al.  Limits to the magnitude of capacitance in carbon nanotube array electrode based electrochemical capacitors , 2013 .