Ethanol-directed morphological evolution of hierarchical CeOx architectures as advanced electrochemical capacitors

To surmount the fundamental limits of energy density in the current supercapacitor devices, the electrode materials should be capable of storing localized charge while having a high degree of freedom to provide ease of electron/ion flow in/out of the electrodes. Herein, we demonstrated a facile approach to designing CeOx based hierarchical architectures for high-performance energy storage electrodes. The unique CeOx based hierarchical architectures, including nanowires, nanocables, nano-micro biscuits and micro walls, were fabricated by simply manipulating the nitrate ion oxidation rate during electrochemical synthesis. Among all the electrodes, the CeOx nano-micro biscuits demonstrated the most excellent electrochemical performance from undergoing fast faradaic reactions leading to high specific capacitance within short charging time. Furthermore, voltammetric sweep mediated analysis was utilized to quantify the capacitive and intercalation effects in the total stored charge capacity of CeOx nano-micro biscuits. The presence of higher Ce3+ content (as confirmed by XPS studies) in CeOx nano-micro biscuits could be responsible for accelerating faradaic redox reactions (conversion of Ce3+ to Ce4+) in electrolyte solution, which is sufficient for realizing their superior performance over the other nano-microstructures. The present study demonstrates the effectiveness of CeOx as a low-cost and promising candidate for future energy storage/harvesting and integrated nanoelectronic devices.

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

[2]  Xinliang Feng,et al.  2D Sandwich‐like Sheets of Iron Oxide Grown on Graphene as High Energy Anode Material for Supercapacitors , 2011, Advanced materials.

[3]  V. Pavarajarn,et al.  Solvothermal Synthesis of ZnO with Various Aspect Ratios Using Organic Solvents , 2006 .

[4]  F. Béguin,et al.  Vanadium nitride/carbon nanotube nanocomposites as electrodes for supercapacitors , 2011 .

[5]  John Wang,et al.  Pseudocapacitive Contributions to Electrochemical Energy Storage in TiO2 (Anatase) Nanoparticles , 2007 .

[6]  S. Selladurai,et al.  Shape controlled synthesis of CeO2 nanostructures for high performance supercapacitor electrodes , 2014 .

[7]  F. Gao,et al.  Water Amount Dependence on Morphologies and Properties of ZnO nanostructures in Double-solvent System , 2014, Scientific Reports.

[8]  S. Selladurai,et al.  Electrochemical capacitance of porous NiO–CeO2 binary oxide synthesized via sol–gel technique for supercapacitor , 2014, Ionics.

[9]  H. Alshareef,et al.  Nanostructured Ternary Electrodes for Energy‐Storage Applications , 2012 .

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

[11]  Ran Liu,et al.  Heterogeneous nanostructured electrode materials for electrochemical energy storage. , 2011, Chemical communications.

[12]  Sean Li,et al.  Voltage sweep modulated conductance quantization in oxide nanocomposites , 2014 .

[13]  B. Dunn,et al.  The Effect of Crystallinity on the Rapid Pseudocapacitive Response of Nb2O5 , 2012 .

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

[15]  Yi Wang,et al.  CeO2 nanoparticles/graphene nanocomposite-based high performance supercapacitor. , 2011, Dalton transactions.

[16]  Sean Li,et al.  Stochastic memristive nature in Co-doped CeO2 nanorod arrays , 2013 .

[17]  S. Khondaker,et al.  Anchoring ceria nanoparticles on reduced graphene oxide and their electronic transport properties , 2011, 1107.1745.

[18]  Amit Kumar,et al.  Luminescence properties of europium-doped cerium oxide nanoparticles: role of vacancy and oxidation states. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[19]  Zhong Lin Wang,et al.  Polyhedral Shapes of CeO2 Nanoparticles , 2003 .

[20]  S. Ivanov,et al.  Role of polymer synthesis conditions for the copper electrodeposition in polyaniline , 2001 .

[21]  G. Muralidharan,et al.  Porous NiO/C Nanocomposites as Electrode Material for Electrochemical Supercapacitors , 2013 .

[22]  John R. Miller,et al.  Electrochemical Capacitors for Energy Management , 2008, Science.

[23]  Chenguo Hu,et al.  Synthesis of Ba-doped CeO2 nanowires and their application as humidity sensors , 2007, Nanotechnology.

[24]  M. Ottmar Advanced Energy Materials to Expand in 2011 , 2010 .

[25]  S. Ardizzone,et al.  "Inner" and "outer" active surface of RuO2 electrodes , 1990 .

[26]  B. Dunn,et al.  High‐Performance Supercapacitors Based on Intertwined CNT/V2O5 Nanowire Nanocomposites , 2011, Advanced materials.

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

[28]  B. Conway,et al.  The role and utilization of pseudocapacitance for energy storage by supercapacitors , 1997 .

[29]  Q. Wang,et al.  Recent Advances in Design and Fabrication of Electrochemical Supercapacitors with High Energy Densities , 2014 .