Effect of the Components of the Electrode on the Pore Texture and Electrochemical Performance of Manganese Dioxide-Based Electrode for Application in Hybrid Electrochemical Capacitor 1

In the 1970s, Conway and others observed that the reversible redox processes occurring at or near the surface of an appropriate electrode material led to electrical double layer capacitor (EDLC)-like electrochemical properties and also a higher charge storage.² Later, Lee and Goodenough were the first to report the pseudocapacitive behavior of manganese dioxide.³ Since that, it has been widely studied as active electrode material for application in aqueous electrochemical capacitors. Due to the low potential stability window of MnO₂-based electrode of about 1V, a hybrid electrochemical capacitor using electrodes with different potential range has been proposed.⁴ Such hybrid electrochemical capacitor can consist of a carbon negative electrode, a manganese dioxide-based positive electrode and a mild neutral electrolyte.⁵

Manganese dioxide is characterized by a theoretical specific capacitance of about 1233 F/g, which is far from being experimentally attainable.⁶ Even for very thin film (< 100 nm) and very low mass (< 100 µg) loading, of MnO₂, the specific capacitance rarely exceeds 1000 F/g.^7-9 On the other hand, in the case of thicker composite electrode and higher loading of MnO₂ the electrochemically addressable material is commonly in the 10 to 20 % range. ^{10, 11} To meet the requirements mentioned above, more fundamentals studies are needed to understand the role of all components of a composite electrode.

Composite electrode based on manganese dioxide, a binder (poly(tetrafluoroethylene, PTFE) and a carbon additive (Acetylene black or high surface area Black Pearls 2000) were characterized by scanning electron microscopy and nitrogen gas adsorption. The electrochemical performances of the MnO₂-Carbon-PTFE composite electrodes materials are evaluated by cyclic voltammetry. Brunauer–Emmett–Teller (BET) surface area measurements indicate that the addition of the PTFE binder does not block access to the porous network of MnO₂ and the two carbon powders. Only acetylene black appears to slightly adversely affect the mesoporous surface, presumably because of its larger particle size compared to Black Pearls 2000. The electrochemical utilization of MnO₂ is similar whether acetylene black or Black Pearls 2000 is used as carbon additive. This suggests that the porosity of Black Pearls, which could perhaps act as a reservoir of ionic species, does not appear to play a significant role as demonstrated by similar specific capacitance at slow scan rate. On the other hand, the effect of additional conductive agent such as acetylene black induces a slight increase of the specific capacitance at high scan rate. Finally, a plot of Coulombic efficiency as a function of the upper positive potential limit showed that using a high surface carbon support with MnO₂ can cancel the effect of the larger potential window of electroactivity of MnO₂ because of its smaller electrochemical potential stability range.

References

 

1.         A. Gambou-Bosca and D. Belanger, Journal of Materials Chemistry A, 2014 DOI: 10.1039/ c3ta14910b.

2.         P. Simon, Y. Gogotsi and B. Dunn, Science, 2014, 343, 1210-1211.

3.         H. Y. Lee and J. B. Goodenough, Journal of Solid State Chemistry, 1999, 144, 220-223.

4.         T. Brousse and D. Bélanger, Electrochemical and Solid-State Letters, 2003, 6, A244-A248.

5.         J. W. Long, D. Bélanger, T. Brousse, W. Sugimoto, M. B. Sassin and O. Crosnier, MRS Bulletin, 2011, 36, 513-522.

6.         M. Toupin, T. Brousse and D. Bélanger, Chemistry of Materials, 2004, 16, 3184-3190.

7.         R. Ranjusha, A. Sreekumaran Nair, S. Ramakrishna, P. Anjali, K. Sujith, K. R. V. Subramanian, N. Sivakumar, T. N. Kim, S. V. Nair and A. Balakrishnan, Journal of Materials Chemistry, 2012, 22, 20465-20471.

8.         Suhasini, Journal of Electroanalytical Chemistry, 2013, 690, 13-18.

9.         T. Bordjiba and D. Bélanger, Electrochimica Acta, 2010, 55, 3428-3433.

10.        P. Staiti and F. Lufrano, Journal of Power Sources, 2009, 187, 284-289.

11.        A. Zolfaghari, H. R. Naderi and H. R. Mortaheb, Journal of Electroanalytical Chemistry, 2013, 697, 60-67.