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Phase-controlled synthesis of polymorphic MnO2

structures for electrochemical energy storage†
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Cite this: DOI: 10.1039/c4ta06943a

Bosi Yin, Siwen Zhang, He Jiang, Fengyu Qu and Xiang Wu*

Manganese dioxide (MnO2) with a-, b- and d-type structures was controllably synthesized by hydrothermal
treatment of an acidic solution of KMnO4 containing different concentrations of ions at 160
C. The effects
of metallic cations, H+ and anions on the structures and morphologies of MnO2 were investigated
systematically. The experimental results indicated that cations played a significant part in the formation
of MnO2 with different structures. When K+ ions were in competition with H+ ions in solution, different
MnO2 structures were formed. a-MnO2 was formed when the amount of K+ was higher than the amount
of H+, whereas a higher amount of H+ was favorable for the growth of b-MnO2 structures. When the
concentration of K+ was much greater than that of H+, d-MnO2 was obtained. Possible formation
mechanisms are proposed based on a series of controlled experiments. The electrochemical properties
of supercapacitors based on different types of MnO2 electrodes were investigated in detail. The specific
capacitance measured for MnO2 strongly depended on the crystallographic structure and decreased in
the order a-MnO2 > d-MnO2 > b-MnO2 at a current density of 0.5 A g1. A specific capacitance of 535 F
Received 17th December 2014
Accepted 14th January 2015
g1 was obtained for a-MnO2, but was only 155 F g1 for b-MnO2. a-MnO2 was more suitable for use as
the working electrode at high current densities. Both a- and d-MnO2 had a poor cycling performance
DOI: 10.1039/c4ta06943a
after 3000 cycles, whereas b-MnO2 showed good stability, maintaining a cycling efficiency of 80% after
[Link]/MaterialsA under the same conditions.

one-, two- or three-dimensional tunnel structures. Different

1. Introduction structures can be described by the size of their tunnels, which
Climate change and the decreasing availability of fossil fuels are determined by the number of octahedral subunits (n  m).
require a move towards sustainable and renewable energy For the a-MnO2 structure, the double chains of edge-sharing
resources. Electrochemical supercapacitors are currently the MnO6 octahedra share corners and form one-dimensional
focus of intense research because they are extremely useful square 2  2 open tunnels with dimensions of 4.6  4.6 Å
energy storage devices that release energy quickly.1–10 Many (Fig. 1b). This large tunnel structure is suitable for the insertion/
materials have been evaluated as active electrodes for electro- extraction of alkali cations.18 A small amount of cations such as
chemical supercapacitors, including carbon-based materials, Li+, Na+, K+, NH4+, Ba2+ or H3O+ is required to stabilize the 2  2
conducting polymers and transition metal oxides.11,12 However, tunnels in a-MnO2. b-MnO2 (Fig. 1c) has 1  1 tunnels formed
their performance needs to be substantially improved to meet by a single strand of edge-sharing MnO6 octahedra. As a result
the future requirements of energy devices, which range from of this narrow 1  1 tunnel size (1.89 Å), b-MnO2 cannot
portable electronics to hybrid electric vehicles. accommodate cations.17 The b-type structure is the most stable
MnO2 is an alternative pseudocapacitive material and has phase of MnO2. d-MnO2 (Fig. 1d) is a two-dimensional layered
attracted much attention because of its high theoretical birnessite structure with an interlayer separation of 7 Å.19 This
capacitance (1370 F g1), low toxicity and low cost.13–16 MnO2 unique two-dimensional structure is characterized by the layer
exists in several crystallographic forms (a, b, g, d and l).17 All the interspacing distance, which depends on the cations and H2O.
MnO2 structures consist of a series of allotropic forms based on The capacitive behavior of MnO2 was rst reported in 1999
octahedral MnO6 building blocks. Oxygen atoms are distributed by Lee and Goodenough.20 They synthesized amorphous
at the corners of the octahedra and the Mn atoms are located in hydrated MnO2 by reacting KMnO4 with Mn(CH3COO)2 and
the center (Fig. 1a). The piling up of MnO6 octahedra builds the found that MnO2-based composite electrodes showed an almost
ideal supercapacitive behavior. There are many other reports on
Key Laboratory for Photonic and Electronic Bandgap Materials, Ministry of Education, the electrochemical properties of MnO2 nanostructures. Yuan
Harbin Normal University, Harbin 150025, P. R. China. E-mail: wuxiang05@gmail. et al.21 reported a novel and highly exible solid-state super-
com capacitor based on carbon nanoparticle/MnO2 nanorod hybrid
† Electronic supplementary information (ESI) available. See DOI: structures fabricated using a simple ame synthesis method
10.1039/c4ta06943a

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2.1 Synthesis of a-MnO2

a-MnO2 nanorods were synthesized in an acidic KMnO4 reac-
tion system. In a typical synthesis, 75 mL of 0.2 M nitric acid
were poured into a 100 mL glass beaker and 12.5 mmol of
KMnO4 were dissolved into this acidic aqueous solution with
constant stirring. The mixed solution was then placed into a
100 mL sealed Teon-lined autoclave and reacted hydrother-
mally at 160
C for 24 h. The autoclave was then cooled naturally
to room temperature and the obtained product was washed
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sequentially with deionized water and ethanol and then dried at

50
C for 12 h in air.

2.2 Synthesis of b-MnO2

b-MnO2 microcrystals were prepared by the same synthesis
route as a-MnO2, but the molar quantity of KMnO4 was
decreased to 3 mmol.

2.3 Synthesis of d-MnO2

d-MnO2 microowers were prepared by the same synthesis
route as a-MnO2, but the amount of KMnO4 was doubled. The
Fig. 1 (a) Three-dimensional diagram of MnO2 crystal cells. Different presence of excess K+ ions stabilized the two-dimensional
crystal structures of MnO2: (b) a-MnO2; (c) b-MnO2; and (d) d-MnO2.
layered d-MnO2.

2.4 Characterization
and electrochemical deposition. Chen et al.22 proposed a
coupled microwave–hydrothermal process to crystallize poly- The crystalline structures of the as-obtained products were
morphs of MnO2. In our previous work, we reported a simple characterized using an X-ray diffractometer (XRD; Rigaku
hydrothermal route for the synthesis of uniform a-MnO2 Dmax-2600/pc, Cu Ka radiation, l ¼ 0.1542 nm, 40 kV, 150 mA).
nanowires using a redox reaction in a MnCl2–KMnO4 aqueous The detailed morphologies of the samples were characterized by
solution system.23 scanning electron microscopy (SEM; Hitachi SU70). The
However, it is still a huge challenge to achieve the desired microstructural characteristics of the products were analyzed by
MnO2 structures with a controlled phase. Few reports have Raman spectrometry (LabRAM HR 800).
focused on the relation between the structure and the elec-
trochemical properties. In the work reported here, we 2.5 Electrochemical measurements
successfully synthesized MnO2 with a-, b- and d-type struc- The electrochemical characteristics of the as-obtained products
tures by controlling the concentration of metallic cations and were studied on a CHI660 electrochemical workstation (Chen-
H+. The effects of different ions on the structures and hua, Shanghai) using cyclic voltammetry, chronopotentiometry
morphologies of MnO2 were systematically investigated. The and electrochemical impedance testing by conguring the
relation between the structure and the electrochemical samples into a three-electrode cell. The samples were used as
properties was studied by evaluating the capacitance of these the working electrode, Pt foil was used as the counter electrode
materials. The results show that the loose tunnel or layer and a saturated calomel electrode was used as the reference
structures (a- and d-type) decrease the effective diffusion path electrode. The electrodes were prepared using high-purity
and increase the effective space for insertion and extraction, battery-grade Ni foil (0.18 mm thick) as the current collector.
which favors the movement of charged particles (ions, elec- The Ni foil was rst cleaned successively with detergent and
trons and protons) in the crystal lattice. The unique structures deionized water. A mixture containing 80 wt% MnO2 sample,
effectively relieve structural destruction and local volumetric 15 wt% acetylene black and 5 wt% polytetrauoroethylene was
variations during the charge/discharge (CD) process, which well mixed and dried under vacuum at 120
C for 5 h. The elec-
leads to good electrochemical properties. trode area was 1 cm2 and the loading density was about 2.0 mg
cm2. The electrolyte was an aqueous solution of 1.0 mol L1 KOH.

2. Experimental section 3. Results and discussion

All the reagents used were of analytical-reagent grade and were The morphologies of the as-obtained products were character-
used without further purication. All the solutions were ized by SEM. Fig. 2 shows typical morphologies of the a-, b- and
prepared in deionized water. Samples of MnO2 with different d-MnO2 with rod-, block- and sphere-like shapes, respectively.
crystal structures were synthesized by the following procedures. The as-synthesized a-MnO2 samples were composed of many

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Fig. 2 SEM images of the different types of as-synthesized MnO2 nanostructures. (a) a-MnO2; (b) b-MnO2; and (c) d-MnO2. (d) XRD pattern of the
as-synthesized MnO2 products.

one-dimensional nanorods with an average diameter of 50 nm the growth of b-MnO2. When the concentration of K+ was far
and lengths of several micrometers (Fig. 2a). Fig. 2b shows that greater than that of H+, d-MnO2 was obtained.
b-MnO2 consists of many irregular microcrystals. Two-dimen- The effects of the anions on the morphology of the nal
sional d-MnO2 exhibits sphere-like shapes composed of inter- product were also studied. We conducted several controlled
tangled thin sheets with thicknesses of 15 nm (Fig. 2c). Fig. 2d experiments substituting H2SO4 and HCl for HNO3. All the
shows the XRD patterns of the three types of MnO2. All the products were a-MnO2 (Fig. S3†), showing that the type of anion
characteristic peaks can be readily indexed to a-, b- and d-type had less effect on the structure and morphology of MnO2. The
MnO2 (PDF card no. 44-0141, no. 24-0735 and no. 18-0802, XRD patterns of the three samples are shown in Fig. S3d.†
respectively). The XRD pattern with sharp and intense diffrac- A possible formation mechanism of the as-prepared prod-
tion peaks indicates that pure MnO2 structures with good ucts is proposed on the basis of these experiment results. Fig. 3
crystallinity were obtained.
To better study the formation of the different types of MnO2
structures, the effects of metallic cations, H+ and anions on the
structures and morphologies of MnO2 were systematically
investigated. The nitric acid concentration (0.2 M) was kept
constant in the experiment. We rst studied the dependence of
the experiment on the concentration of K+ ions. When the
amount of K+ ions was 3 mmol, b-MnO2 was obtained
(Fig. S1a†). With the amount of K+ ions was increased to
12.5 mmol, a-MnO2 was formed (Fig. S1b†). d-MnO2 can be
prepared by increasing the amount of K+ ions to 25 mmol
(Fig. S1c†). The corresponding XRD patterns are shown in
Fig. S1d.† The effect of the nitric acid concentration on the
crystal phase of the product was then investigated. When the
concentration of H+ increased from 0.05 to 0.2 to 1 M, the crystal
type was transformed from d- to a- and then to b-MnO2 (Fig. S2a,
S2b and S2c†). Fig. S2d† shows the XRD patterns of the three
phases of MnO2. These results indicate that the cations exert a
crucial inuence on the formation of the different MnO2
structures. K+ was in competition with H+ in the reaction
process. a-MnO2 was formed when the amount of K+ was higher Fig. 3Schematic diagram of the growth of the three different MnO2
than that of H+, whereas high amounts of H+ were favorable for products.

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shows a schematic diagram of the growth of the products. First,

a large number of tiny primary MnO2 nuclei are formed as a
result of the decomposition of the KMnO4 molecules under
hydrothermal conditions. Further aggregation of these nuclei
induces the formation of MnO2 precursors. The dissolution–
recrystallization process of the MnO2 precursor is affected by
the K+ and H+ ions in the solution. The radius of K+ coincides
with the 2  2 tunnel size, so K+ can be inserted into the tunnel
of the MnO2 nanostructures and evolves into a stable a-phase
structure.24 However, the presence of H+ may prevent K+ from
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participating in the template reaction of MnO2. High concen-

trations of H+ will greatly reduce the opportunities for K+ to
occupy the active site of the 2  2 tunnel, so highly acidic
conditions favor the generation of the 1  1 tunnel structure.
However, when the concentration of K+ is far greater than that
of H+, too much K+ will lead to destruction of the 2  2 struc-
Fig. 4 Raman spectra of the as-synthesized products. tures. Thus MnO2 nanosheets together with K+ form layered
d-MnO2 structures held together by electrostatic forces.24,25

Fig. 5 CV and galvanostatic CD curves of three different types of MnO2 nanostructures as pseudocapacitor materials in aqueous KOH elec-
trolyte. (a and b) a-MnO2, (c and d) b-MnO2 and (e and f) d-MnO2.

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(a) EIS spectra of the three MnO2 electrodes. (b) CD curves at current densities of 1.0 A g1. (c) CV curves at scan rates of 100 mV s1. (d)
Fig. 6
Dependence of the specific capacitance on the current density.

Fig. 4 shows the Raman spectra of the three types of MnO2 MnO2 + H2O + xK+ + (x + 1)e 4 KxMnOOH + OH (1)
structures. The diffraction peaks at 645 cm1 correspond well
with the Raman spectrum of MnO2 and can be attributed to the
MnO6 symmetric stretching vibrations.26 d-MnO2 consists of The second mechanism is a surface process involving the
layered sheets of MnO6 octahedra and the peak at 573 cm1 adsorption/desorption of alkali cations:
might come from Mn–O stretching in the basal plane of the
MnO6 sheet.27 (MnO2)surface + M+ + e 4 (MnOOM)surface
The electrochemical properties of the three different types (M+ ¼ Li+, Na+, K+ or H3O+) (2)
of MnO2 nanostructures were studied by cyclic voltammetry
It can be seen from eqn (1) and (2) that both the cations and
(CV), galvanostatic CD and electrochemical impedance spec-
the electrons take part in the redox reactions of the MnO2
trometry (EIS) in a three-electrode conguration. Fig. 5 shows
nanostructures. Therefore it can be concluded that the degree
the cyclic voltammograms and corresponding CD curves of
of diffusion of the cations on the surface affects the pseudoca-
the three different MnO2 nanostructures used as electrode
pacitive performance of the electrodes.30,31
materials in aqueous KOH electrolyte. As the current density
Fig. 6 compares the electrochemical performance of three
is one of the most important parameters controlling the
different types of MnO2 nanostructures used as electrode
capacitive performance of the electrode, the CD curves of the
materials. Fig. 6a shows the Nyquist plots of the MnO2 electrode
three types of MnO2 were recorded at different current
in KOH aqueous solution. These measurements were carried
densities. All the CV curves deviate from a rectangular shape
out at room temperature in the frequency range 0.1 Hz to
because of the overpotential and the corresponding CD curves
100 kHz with an open circuit voltage at an AC amplitude of
deviate from symmetrical behavior under different current
5 mV. In the Nyquist plot, the intercept at the real part (Z0 ), Rs,
densities. The CD curves at low current densities show a
which indicates the resistance of the electrochemical system, is
platform corresponding to the redox reactions. There are two
a combination of the ionic resistance of the electrolyte, the
mechanisms for charge storage by MnO2. The rst involves
intrinsic resistance of the substrate, the intrinsic resistance of
the intercalation/extraction of protons (H3O+) or alkali cations
the active material and the contact resistance at the active
such as Li+, Na+ or K+ into the bulk of the oxide particles with
material/current collector interface.14 From the intercepts at the
the concomitant reduction/oxidation of Mn ions:28,29
real axis at high frequency it can be seen that Rs decreases in the

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Fig. 7 Dependence of the cycling performance on the current density: (a) a-MnO2, (d) b-MnO2 and (g) d-MnO2. Cycle life of the MnO2
electrode: (b) a-MnO2, (e) b-MnO2 and (h) d-MnO2. Last ten cycles of the MnO2 CD curves at a current density of 1 A g1: (c) a-MnO2, (f) b-MnO2
and (i) d-MnO2.

order a-MnO2 z d-MnO2 > b-MnO2. All the MnO2 structures electrochemical properties and capacitive behavior of the
show a low impedance as pseudocapacitors (<1.5 U), indicating supercapacitor electrodes were evaluated by CV and galvano-
the good electrical conductivity of the devices. The semicircle static CD. The specic capacitance (SC) and capacitance (F g1)
diameter reects the charge-transfer resistance (Rct), which of the electrode material were calculated from the galvanostatic
results from electron diffusion. Rct can be calculated from the discharge according to the equation
diameter of the semicircle in the high frequency range. This is
also called the Faraday resistance, which is a factor affecting the C ¼ IDt/(DVm)
specic power of the supercapacitor.32 The Warburg resistance
(Rw), which describes the diffusion of redox species in the where I is the discharge current (A), Dt is the discharge time (s),
electrolyte, is reected by the slope of the EIS curve in the low DV is the voltage change (V), excluding the IR drop in the
frequency range.33 This range corresponds to the diffusion- discharge process, and m is the mass of the active material (g).
limited mechanism. Galvanostatic CD measurements of the Fig. 6d summarizes the SC vs. current density relation for the
MnO2 electrode were carried out to further assess its potential three different types of MnO2 pseudocapacitor. An SC value of
as an electrode material. Fig. 6b compares the CD behavior of all 535 F g1 was obtained for a-MnO2, whereas it was 464 and
three types of electrode at a constant current density of 1 A g1. 155 F g1 for d-MnO2 and b-MnO2, respectively. a-MnO2 has a
At the same scan rate of 100 mV s1, the integrated area of the one-dimensional structure with 2  2 tunnels, whereas d-MnO2
CV loops increases in the order b-MnO2 < d-MnO2 < a-MnO2 has a two-dimensional layered structure. Alkali cations or
(Fig. 6c), which agrees with the behavior of the CD curves, for protons can be intercalated into the wide 2  2 tunnels (about
which the CD time increases in the same order (Fig. 6b). The 4.6 Å) of a-MnO2 (ref. 19) and in between the layers (about 7 Å)

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of two-dimensional d-MnO2.21 The high SC values (Fig. 6d) of 3 L. N. Gao, X. F. Wang, Z. Xie, W. F. Song, L. J. Wang, X. Wu,
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a-MnO2 and between the layers of d-MnO2. Because b-MnO2 has 4 P. H. Yang and W. J. Mai, Nano Energy, 2014, 8, 274–290.
narrow 1  1 sized tunnels, the amount of alkali cations 5 X. F. Wang, X. H. Lu, B. Liu, D. Chen, Y. X. Tong and
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protons cannot easily be inserted into narrow 1  1 tunnels 6 Y. Jiao, Y. Liu, B. S. Yin, S. W. Zhang, F. Y. Qu and X. Wu,
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cations or protons.34 Hence the observed SC is only 155 F g1 for 7 Y. Liu, Y. Jiao, B. S. Yin, S. W. Zhang, F. Y. Qu and X. Wu, J.
Published on 14 January 2015. Downloaded by University of Louisville on 04/02/2015 06:25:59.

b-MnO2. Fig. 7a shows that the cycling performance of a-MnO2 Mater. Chem. A, 2015, DOI: 10.1039/c4ta06339b.
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