Effect of Crystallographic Structure of MnO2 on Its Electrochemical Capacitance Properties

MnO2 is currently under extensive investigations for its capacitance properties. MnO2 crystallizes into several crystallographic structures, namely, α, β, γ, δ, and λ structures. Because these structures differ in the way MnO6 octahedra are interlinked, they possess tunnels or interlayers with gaps of different magnitudes. Because capacitance properties are due to intercalation/deintercalation of protons or cations in MnO2, only some crystallographic structures, which possess sufficient gaps to accommodate these ions, are expected to be useful for capacitance studies. In order to examine the dependence of capacitance on crystal structure, the present study involves preparation of these various crystal phases of MnO2 in nanodimensions and to evaluate their capacitance properties. Results of α-MnO2 prepared by a microemulsion route (α-MnO2(m)) are also used for comparison. Spherical particles of about 50 nm, nanorods of 30−50 nm in diameter, or interlocked fibers of 10−20 nm in diameters are formed, which d...

[1]  W. H. Baur.  Rutile-type compounds. V. Refinement of MnO2 and MgF2 , 1976 .

[2]  Y. Sun,et al.  Factors influencing the structure of electrochemically prepared α-MnO2 and γ-MnO2 phases , 2007 .

[3]  R. Reddy,et al.  Sol–gel MnO2 as an electrode material for electrochemical capacitors , 2003 .

[4]  Jim P. Zheng,et al.  A New Charge Storage Mechanism for Electrochemical Capacitors , 1995 .

[5]  N. Munichandraiah,et al.  Synthesis and Characterization of Nano- MnO2 for Electrochemical Supercapacitor Studies , 2008 .

[6]  Nae-Lih Wu,et al.  Investigation of Pseudocapacitive Charge-Storage Reaction of MnO2 ∙ nH2O Supercapacitors in Aqueous Electrolytes , 2006 .

[7]  Pierre-Louis Taberna,et al.  Long-term cycling behavior of asymmetric activated carbon/MnO2 aqueous electrochemical supercapacitor , 2007 .

[8]  N. Munichandraiah,et al.  The Effect of Nonionic Surfactant Triton X-100 during Electrochemical Deposition of MnO2 on Its Capacitance Properties , 2007 .

[9]  Jun Chen,et al.  Facile controlled synthesis of MnO2 nanostructures of novel shapes and their application in batteries. , 2006, Inorganic chemistry.

[10]  P. M. D. Wolff.  Interpretation of some γ‐MnO2 diffraction patterns , 1959 .

[11]  Yong Yang,et al.  Preparation and Properties of Manganese Oxide/Carbon Composites by Reduction of Potassium Permanganate with Acetylene Black , 2007 .

[12]  B. V. Tilak,et al.  Materials for electrochemical capacitors: Theoretical and experimental constraints , 1996 .

[13]  Mathieu Toupin,et al.  Crystalline MnO2 as Possible Alternatives to Amorphous Compounds in Electrochemical Supercapacitors , 2006 .

[14]  S. Wong,et al.  Synthesis and characterization of pillared buserite , 1992 .

[15]  A. Burke.  Ultracapacitors: why, how, and where is the technology , 2000 .

[16]  Michael M. Thackeray,et al.  Manganese oxides for lithium batteries , 1997 .

[17]  A. Manthiram,et al.  Synthesis of Manganese Oxides by Reduction of KMnO4with KBH4in Aqueous Solutions , 1998 .

[18]  O. Bricker,et al.  Some stability relations in the system Mn-O2-H2O at 25° and one atmosphere total pressure , 1965 .

[19]  Q. Feng,et al.  Hydrothermal Soft Chemical Process for Synthesis of Manganese Oxides with Tunnel Structures , 1998 .

[20]  R. Ma,et al.  Layered MnO2 Nanobelts: Hydrothermal Synthesis and Electrochemical Measurements , 2004 .

[21]  D. Guyomard,et al.  One-Step Electrochemical Synthesis of α ­ MnO2 and α ⋅ γ ­ MnO2 Compounds for Lithium Batteries , 2001 .

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

[23]  L. Bulhões,et al.  An EQCM investigation of charging RuO2 thin films prepared by the polymeric precursor method , 2005 .

[24]  Arumugam Manthiram,et al.  Nanocrystalline Manganese Oxides for Electrochemical Capacitors with Neutral Electrolytes , 2002 .

[25]  Yadong Li,et al.  Synthesis and formation mechanism of manganese dioxide nanowires/nanorods. , 2003, Chemistry.

[26]  P. Ajayan,et al.  Hydrothermal synthesis and pseudocapacitance properties of MnO2 nanostructures. , 2005, The journal of physical chemistry. B.

[27]  J. C. Hunter.  Preparation of a new crystal form of manganese dioxide: λ-MnO2 , 1981 .

[28]  John B. Goodenough,et al.  Supercapacitor Behavior with KCl Electrolyte , 1999 .

[29]  S. W. Kim,et al.  Expansion of Active Site Area and Improvement of Kinetic Reversibility in Electrochemical Pseudocapacitor Electrode , 2001 .

[30]  S. Suib,et al.  A Review of Porous Manganese Oxide Materials , 1998 .

[31]  G. Rossman,et al.  The tetravalent manganese oxides: identification, hydration, and structural relationships by infrared spectroscopy , 1979 .

[32]  Jim P. Zheng,et al.  Hydrous Ruthenium Oxide as an Electrode Material for Electrochemical Capacitors , 1995 .

[33]  M. Anderson,et al.  Novel Electrode Materials for Thin‐Film Ultracapacitors: Comparison of Electrochemical Properties of Sol‐Gel‐Derived and Electrodeposited Manganese Dioxide , 2000 .

[34]  Jim P. Zheng,et al.  Ruthenium Oxide‐Carbon Composite Electrodes for Electrochemical Capacitors , 1999 .

[35]  S. Suib,et al.  Manganese Oxide Octahedral Molecular Sieves: Preparation, Characterization, and Applications , 1993, Science.

[36]  N. Munichandraiah,et al.  Electrochemical Supercapacitor Studies of Nanostructured α-MnO2 Synthesized by Microemulsion Method and the Effect of Annealing , 2007 .

[37]  Mathieu Toupin,et al.  Influence of Microstucture on the Charge Storage Properties of Chemically Synthesized Manganese Dioxide , 2002 .

[38]  N. Munichandraiah,et al.  High Capacitance of Electrodeposited MnO2 by the Effect of a Surface-Active Agent , 2005 .

[39]  Mathieu Toupin,et al.  Charge Storage Mechanism of MnO2 Electrode Used in Aqueous Electrochemical Capacitor , 2004 .