212th ECS Meeting, Abstract #339, The Electrochemical Society

Kyung-Wan Nam1, Sang-Bok Ma2, Kwang-Bum Kim2,

Won-Sub Yoon1, James McBreen1, and Xiao-Qing Yang1
1

Chemistry Department, Brookhaven National

Laboratory, Upton, New York 11973, USA

Material Science and Engineering Division, Yonsei

University, Seoul, Korea

Supercapacitors are gaining more attentions recently

as energy storage devices, particularly in applications for
systems requiring high power re. Potential applications
include secondary power supply to the primary power
sources such as batteries and fuel cells in hybrid electric
vehicle (HEV) or fuel cell electric vehicle (FCEV)
propulsion, for power and cycle life enhancement. In the
past decade, most of the research on electrode materials
for supercapacitors has been focused on transition metal
oxides such as RuO2, NiOx, V2O5 and MnO2 in aqueous
electrolytes.1~4 However, supercapacitors using aqueous
electrolytes suffer from a low specific energy density
(Wh/kg) because of a small potential window of
approximately 1 V. Recently, Ma et al. reported their
work on synthesizing MnO2/CNT (carbon nanotube)
nanocomposite by spontaneous direct redox deposition5
and their studies on electrochemical properties of these
electrodes in organic electrolyte for supercapacitor
application6 The MnO2/CNT nanocomposite electrode
showed quite promising specific capacitance over 500F/g
in the organic electrolyte within 3.5 ~ 1.5V vs. Li 6
Unfortunately, the crystallinity of MnO2/CNT
nanocomposite material used for supercapacitor is rather
low, due to the lack of long range ordering of the MnO6
octahedral framework.5 The close to amorphous nature
results in broad XRD peaks and makes it very difficult to
study the structural changes during the charge-discharge
cyclings. On the other hand, X-ray absorption
spectroscopy (XAS) is a technique that is atomic specific
and capable of probing the short to medium range
structures around the absorbing element, regardless the
existence of the long range ordering. Therefore, XAS can
be used as a powerful tool for the local structural change
studies during the charge-discharge cyclings of MnO2/
CNT nanocomposite electrodes. In this work, we report
our results of XAS studies on the mechanism for the
electrochemical process of the MnO2/CNT supercapacitor
material cycled in organic electrolyte.
MnO2/CNT nanocomposite was synthesized by a
direct redox reaction between the CNTs and MnO4-.
Manganese dioxide can be spontaneously deposited on
the CNT surface by using this method.5 In situ Mn Kedge XAS measurements were carried out in transmission
and fluorescence modes at beamline X19A of the
National Synchrotron Light Source (NSLS) using a
Si(111) double-crystal monochromator detuned to ~ 50%
of its original intensity, in order to eliminate the high
order harmonics. Energy calibration was done by using
the first inflection point of the spectrum of Mn metal foil
as a reference (i.e., Mn K-edge = 6539 eV). Reference
spectra were simultaneously collected for each in situ
spectrum by using Mn metal foil.

Figure 1 shows Mn K-edge XANES spectra of

MnO2/CNT electrode during the first discharge from 4.0V
to 1.5V. In every XANES spectrum shown in Fig. 1, there
is a weak absorption pre-edge peak and a strong main
edge absorption peak. The weak pre-edge absorption was
attributed to the electric dipole forbidden transition of a 1s
electron to an unoccupied 3d orbital, which is partially
allowed because of electric quadrupole coupling and/or
3d-4p orbital mixing arisen from the noncentrosymmetric
environment of the slightly distorted MnO6 octahedral
framework. The main absorption edge features were
assigned to the purely dipole-allowed 1s 4p transition.
It should be noted that the XANES spectra show clear
shift to lower energies during discharge. This entire edge
shift to the lower energies indicates that the average
oxidation state of manganese ions decreases during
discharge. From this result, it is concluded that the
capacitance of MnO2/CNT nanocomposite electrode
originates from the Faradaic redox pseudocapacitance
rather than the double layer capacitance.
1.6

Normalized Intensity (a. u.)

In Situ X-ray Absorption Spectroscopic Studies of

MnO2/CNT Nanocomposite Electrodes for
Supercapacitors

1.2

6535

6540

6545

6550

Photon Energy ( eV )

0.8

0.4

4.0V
3.1V
2.0V
1.5V

0.0
6530

6540

6550

6560

6570

Photon Energy ( eV )

Fig. 1. In situ Mn K-edge XANES spectra of

MnO2/CNT electrode during the first discharge
from 4.0 to 1.5V vs. Li.
Detailed local structure changes of MnO2/CNT
electrodes during the long term cycling with high rate will
also be presented at the meeting.
Acknowledgment
The work at Brookhaven National Lab. was
supported by the Assistant Secretary for Energy
Efficiency and Renewable Energy, Office of
FreedomCAR and Vehicle Technologies of the U.S. DOE
under Contract No. DE-AC02-98CH10886.
References
1. J. P. Zheng, P. J. Cygan, and T. R. Zow, J. Electrochem.
Soc., 142, 2699 (1995).
2. K. W. Nam, and K. B. Kim, J. Electrochem. Soc., 153,
A81 (2006).
3. H. Y. Lee, and J. B. Goodenough, J. Solid State Chem.,
148, 81 (1999).
4. S. C. Pang, M. A. Anderson, and T. W. Chapman, J.
Electrochem. Soc., 147, 444 (2000).
5. S.-B. Ma, K.-Y. Ahn, E.-S. Lee, K.-H. Oh, and K.-B.
Kim, Carbon, 45, 375 (2007).
6. S.-B. Ma, and K.-B. Kim, in The 210th Electrochemical
Society Meeting in Cancun, Mexico, abstract B2200,
Oct 29-Nov.3, (2006).

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