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Effect of morphology of manganese oxide on the capacitive behavior of

electrodes
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Page 1 of 21 AUTHOR SUBMITTED MANUSCRIPT - MRX-118497.R1

1
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3 Effect of morphology of Manganese oxide on the capacitive behavior of electrodes
4
5 *
Zaeem Ur Rehman, Mohsin Ali Raza, Aoun Hussnain, Uzair Naveed Chishti, Aqil Inam,
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7 Farasat Ali, Muhammad Faheem Maqsood,
8

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9 Department of Metallurgy & Materials Engineering, University of the Punjab, Lahore,
10
Pakistan.
11
12 *
Corresponding author email: zaeemurrehman6@gmail.com
13

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14 Abstract
15
16 Manganese oxide (MnO2) was synthesized by reduction of potassium permanganate followed by
17 calcination in air at 200, 400 and 600 °C. Morphology and structure of MnO2 was characterized
18
19 by scanning electron microscopy and x-ray diffraction, respectively. Electrochemical
20

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21 characterization of MnO2-based electrodes was carried out by cyclic voltammetry (CV),
22
23 galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS). CV results
24 revealed that MnO2-based electrode calcined at 200 °C showed maximum specific capacitance
25
26 of 177 F/g at a scan rate of 1 mVs-1 in 3M potassium hydroxide. EIS analysis of electrode
27
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produced with MnO2 that was calcined at 200 °C showed solution resistance and charge transfer

30 resistance values of 0.421 and 1.605 Ω, respectively. CV results also revealed that MnO2-based
31
electrodes showed capacitance retention of 89 % at 50 mVs-1 scan rate for 1000 cycles.
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36 Keywords: Morphology; Manganese oxide; Supercapacitor electrodes; Electrochemical
37
38 characterization; Specific capacitance.
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1
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3 1. Introduction
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5 The alarming environmental concerns and the depletion of natural reserves of fossil fuels have
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7 increased the need to find alternative methods for power generation to meet the rising energy
8
demand. The ideal way to overcome these issues is the use of renewable energy [1-5]. However,

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10 the renewable sources also require an effective means of energy storage. Energy storage
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12 devices such as batteries and supercapacitors (SCs) are essentially required to effectively
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14 integrate electrical energy into the grid system [6-9].
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SCs are quite attractive and provide exceptional features such as higher power density, power
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17 capability, fast charging and slow discharging rates, longer life and excellent cyclic stability
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19 [10-14]. Furthermore, supercapacitors also enjoy the benefit of being lightweight, cost
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21 effective, maintenance free and non-toxic in nature. SCs can thus be employed not only for a
22 large number of heavy applications such as in electric cars, buses and light rail transits but also
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24 for various small scale applications such as watches, camera flashes and computer RAMs. [15-
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26 19].
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SCs are characterized into two types depending on the charge storage mechanism, the pseudo-
capacitors or electric double-layer capacitors (EDLCs). In pseudo-capacitors the charge is
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31 stored due to reversible faradaic redox reactions near the surface of electrode or by ion
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33 intercalation in electrode material without a phase change [20-22]. In the latter type, the
34
mechanism for energy storage involves the electrostatic accumulation of charge on the
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36 electrode surface and electrolyte interface [23]. EDLCs are carbon based SCs which provide
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38 better cyclic stability, while pseudo-capacitors are transition metal oxide/metal sulphides/metal
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40 hydroxides or conducting polymers-based which provide higher capacitance. The combination
41 of both can be realized and achieved for optimum properties [24-28].
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The major drawback of supercapacitors is that they provide low energy density, however, this
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45 can be overcome by enhancing the voltage window or capacitance [29]. The capacitance can
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be increased by increasing surface area, reducing particle size, producing defects, tailoring with
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48 oxygen content in structure or by doping [30]
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50 Recent research in the field of SCs is focusing on development of novel pseudo-capacitor
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52 electrode materials as they have potential to provide higher values of capacitance. There are
53 many candidate materials like MnO2, RuO2, TiO2, polyaniline (PANI) or polypyrrole [30, 31].
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55 However, the most significant one is manganese oxide (MnO2) because of its low cost,
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57 abundance and eco-friendly nature. It also offers, a remarkable theoretical specific capacitance
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59
(Cs) of about 1110-1370 F/g [32-34]. The only disadvantage of MnO2 as a SC electrode
60 material is its low electrical conductivity and poor capacity [35-37]. Theoretical Cs of MnO2
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Page 3 of 21 AUTHOR SUBMITTED MANUSCRIPT - MRX-118497.R1

1
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3 can never be achieved due to low conductivity of MnO2. However, Cs of MnO2 can be
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5 improved by designing and engineering the electrode structure, morphology and size of MnO2
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7 as these factors increase the sites for electrochemical redox reactions and thus increase the
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capacitance.

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10 MnO2 can have various morphologies such as flakes, nanosheets, nanotubes, nanoflowers and
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12 thin films all depending on the mode of synthesis [36, 38-40]. Ming et al. [41] prepared
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14 ultrathin arrays of MnO2 on nickel foam by hydrothermal approach. The prepared electrodes
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showed maximum Cs of 595 F/g at 0.5 A/g current density with 89 % charge retention and 64
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17 % charge capability in 1 M KOH electrolyte. Wu et al. [42] prepared MnO2 with 4 distinct
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19 crystal structures using different parameters via hydrothermal process. MnO2 having a micro-
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21 flower nanostructure showed better electrochemical properties of 185 F/g at 0.5 A/g in 1 M
22 Na2SO4 with 100% columbic efficiency. Wu et al. [43] synthesized plate like MnO2 with a 3-
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24 D architecture supported on nickel foam hydrothermally. The prepared electrodes showed Cs
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26 of ca. 681 F/g at 1 mVs-1 scan rate with 91% charge retention in 6 M KOH electrolyte. Sankar
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et al. [44] produced MnO2 by reduction of KMnO4. Reduction time of 15 and 30 min yielded
mesoporous δ-MnO2 and α-MnO2 spherical nanoparticles, respectively. α-MnO2 coated on
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31 stainless steel substrate proved to be a good electrode material. It showed 72% cyclic stability
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33 and achieved Cs of 136 F/g at a current density of 0.5 A/g in 1 M Na2SO4 aqueous electrolyte.
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This research work aims to synthesize MnO2 by reduction of KMnO4 followed by calcination
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36 at different temperatures to obtain different morphologies of MnO2. The effect of morphology
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38 and crystal structure on the electrochemical and capacitive behavior of MnO2-based electrodes
39
40 are studied.
41 2. Experimental
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2.1 Materials
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45 Potassium permanganate (KMnO4), aniline (C6H5NH2), potassium hydroxide (KOH),
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polyvinylidene fluoride (PVDF) and dimethylformamide (DMF) were purchased from Sigma
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48 Aldrich, USA. Carbon black (CB) [Vulcan XC72] was purchased from Cabot Corp., USA and
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50 nickel (Ni) foam was purchased from Winfay Group Co. Ltd., China.
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52 2.2 Synthesis of MnO2

53 The active material was prepared in a beaker by dissolving 9.48 g of KMnO4 in 450 ml de-
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55 ionized (DI) water. KMnO4 was completely dissolved in solution using magnetic stirring for
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57 10 minutes. A purple homogeneous mixture was attained. Then 3 ml aniline was poured drop
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59
wise into the KMnO4 solution. Addition of aniline increased the viscosity of solution, changed
60 the color of solution to blackish brown and reduced the KMnO4 to MnO2 and other by-products
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1
2
3 as shown in the eq. 1 [44]. Further, oxidation and reduction half-cell reactions are given in eq.
4
5 (2 & 3)
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7 𝟐𝐊𝐌𝐧𝑶𝟒 + 𝑪𝟔 𝑯𝟓 𝑵𝑯𝟐 → 𝑪𝟔 𝑯𝟓 𝑵𝑶𝟐 + 𝟐𝑴𝒏𝑶𝟐 + 𝟐𝑲𝑶𝑯 (1)
8
Where KMnO4 is reduced and aniline oxidized. Oxidation and reduction reactions are as

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10 follows:
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12 2Mn+7 + 6e− → 2Mn+4 (Reduction) (2)
13 N −3 H2+2 → N+3 O−4
2 + 6e
−
(Oxidation) (3)

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15 The solution was magnetically stirred for another 10 min for complete reduction of KMnO4.
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17 The solution was then transferred into tubes and was sonicated and centrifuged with alternative
18 rinsing cycle using alcohol and DI water; the supernatant was drained to remove the
19
20 unfavorable by-products. This step was repeated 20 times to achieve a transparent supernatant.

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22 The MnO2 precipitates were transferred into a petri dish for drying in an oven at 70 °C for 3
23
24
hours. Bulky MnO2 agglomerates were obtained which were crushed and ground using a mortar
25 and pestle after which MnO2 powder was divided into three parts and calcined in a tube furnace
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at 200, 400 and 600 °C for 18 hours. Schematic of MnO2 synthesis process is shown in Fig. 1.

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58 Fig. 1. Schematic of MnO2 synthesis.
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3 2.3 Preparation of electrodes
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5 The powders calcined at different temperatures were mixed with CB and PVDF (already
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7 prepared in DMF solution) in a high speed vacuum centrifuge mixer to obtain a homogeneous
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slurry. The slurry was composed of nearly 90% active material, 10% CB and a negligible

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10 quantity of binder (PVDF). For preparation of electrodes, Ni foam was cleaned in ethanol
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12 solution to remove any impurities.
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14 After drying, Ni foam was placed in the container with slurry and mixed using vacuum
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16 centrifuge mixer to ensure uniform coating of MnO2 on porous Ni foam. The coated electrodes
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18 were dried in an oven at 80 °C for 4 hours. Samples were weighed before and after coating to
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calculate deposited weight of MnO2. Schematic of electrode preparation is shown in Fig. 2.

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32 Fig. 2. Schematic representation of electrode preparation.
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34 3. Characterization
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36 3.1 Structural Characterization
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38 X-ray diffraction (XRD) was carried out for structural analysis of MnO2. XRD was conducted
39 with diffractometer (Equinox 2000 of Thermo Fisher Scientific, USA) equipped with curved
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41 position sensitive detector using Cu Kα1 radiations produced using Ge monochromator.
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43 Scanning electron microscopy (SEM) [Inspect S50 of Thermo Fisher Scientific, USA].
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Analysis was conducted on MnO2 powders and coated Ni foam.
46 3.2 Electrochemical characterization
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48 Electrochemical characterization was carried out in a three-electrode cell, in which MnO2
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50 coated Ni foam acted as a working electrode, graphite as a counter electrode and Hg/HgO as a
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reference electrode, using potentiostat/galvanostat/ZRA (Reference 3000, Gamry Instruments,

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53 USA). Cyclic voltammetry (CV) of samples was performed at 1, 5, 10 and 50 mVs-1 scan rates
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55 between a potential range of 0-0.45V in 3 M KOH solution. Cs of MnO2 samples was calculated
56
from CV curves using eq.4 [45]:
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1
2
3 𝑎
4 ∫𝑏 𝐼(𝑉)𝑑𝑉 1
5
Cs = × (4)
2×∆𝑉×𝑣 𝑚
6
𝐚
7 Where the ∫𝐛 𝐈 (𝐕)𝐝𝐕 is area under the CV curve representing charge (C) between the upper
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9 and lower boundaries, 𝚫𝐕 is the potential window in volts (V), m is the mass of active
10
11 material deposited on the Ni foam in grams (g) and 𝛎 is the scan rate in mVs-1.
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Galvanostatic charge discharge (GCD) was carried out at 1, 3, 5 and 10 A/g for 1000 cycles.

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14 Cs from the GCD curve is calculated using eq. 5 [45].
15
16 𝐼 𝑡
17 Cs = × (5)
𝑚 ∆𝑉
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20 Where I is the current in amperes (A), t is discharging time in sec.

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EIS was carried out between a frequency range of 1 mHz to 100 KHz using three electrode
22
23 system as explained above.
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25 The energy and power densities can be calculated from the following equations [46]:
26 1
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𝐸= 7.2
3600
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× 𝑉 2 × 𝐶𝑠 (6)

29 𝑃=𝐸× (7)
𝑡
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31 Where V is voltage window, Cs is specific capacitance, E is energy density and t is discharge
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33 time.
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35 4. Results & discussion
36 4.1 XRD analysis
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38 XRD patterns of MnO2 calcined at different temperatures are shown in Fig. 3. MnO2 calcined
39
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at 200 °C has no definite peaks confirming its amorphous nature. Increasing the calcination
41 temperature improved crystallinity as sharper and more defined peaks were obtained at both
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43 400 and 600 °C. Peaks at 2θ = 38°, 43°, 52°, 64° and 71° with respective planes (211), (301),
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(411), (521) and (541) suggests the formation of α-MnO2 [44, 45]. The peaks were cross
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46 matched with the reference pattern (COD database entry no. = 96-151-4102) and presence of
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48 both MnO2 as a major phase and Mn3O4 as a secondary phase were confirmed. Mn3O4 can be
49 present due to the incomplete oxidation of MnO2 [47].
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51 4.2 SEM analysis
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Morphology of MnO2 powders calcined at different temperatures is shown in Fig. 4 (a-c).
54 MnO2 calcined at 200 °C has flake like morphology with an average size of about 2.5 µm as
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56 shown in Fig. 4 (a). These flakes are irregularly shaped with nearly curved edges.
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Figure 4 (b) shows nanowires formation at the surface of granules/flakes showing an
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59 intermediate structure. By increasing temperature to 400 °C the granular flake-like morphology
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3 of MnO2 is diminished, favoring the formation of nanowires with larger diameters and shorter
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5 lengths. The average flake size reduced, and the structure consists of both nanowires and flaky
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7 MnO2. Further increase in temperature to 600 °C improves crystallinity of MnO2 as determined
8 by XRD (Fig. 3).

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Fig. 3. XRD analysis of MnO2 calcined at 200, 400 and 600 °C.
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The morphology of MnO2 (calcined at 600 °C) clearly shows the formation of long and thin
49 nanowires (Fig. 3(c)). Average diameter and length of these nanowires was found to be 170
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nm and 8 µm. Figure 4 (c) also shows some chunks of MnO2 nanowires agglomerated together.
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53 The as formed nanowires are straight and needle-like. Fig. 4 (d) shows SEM image of MnO2
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(calcined at 200 °C) coated Ni foam. It can be seen that MnO2 is uniformly coated on Ni foam
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56 surface while MnO2 particles are also entrapped in the porous structure of Ni foam.
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3 4.2 CV analysis
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5 4.2.1 Effect of scan rate
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7 Scan rate in CV has prominent effect on capacitive behavior of MnO2. At higher scan rates the
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diffusion of ions and fast redox reactions only occurs at the surface decreasing the C s of the

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10 prepared electrodes. At lower scan rates, enough time is available for the electrolyte ions to
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12 penetrate the porous Ni foam and MnO2, thus increasing the diffusion and hence the area for
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14 reaction [48]. Higher diffusion rate of MnO2 in and out of the Ni foam would result in pseudo-
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capacitive charge storing mechanism because of increased ion intercalation and redox
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17 reactions.
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58 Fig. 4. SEM images of MnO2 calcined at (a) 200 °C (amorphous), (b) 400 °C (semi-
59 crystalline, (c) 600 °C (crystalline) and (d) MnO2 coated Ni foam.
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3 CV curves of MnO2 electrodes calcined at different temperatures at scan rates 1, 5, 10 and 50
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5 mVs-1 are shown in Fig. 5 (a-c). Cs values calculated from CV curves of MnO2 calcined at
6
7 various temperatures and performed at various scan rates are presented in Table 1. Cs vs. scan
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rate graph of MnO2 calcined at various temperatures is shown in Fig. 5(d). This graph shows

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10 that scan rate has an inverse relation with Cs.
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Fig. 5 (a), (b), (c) are CV curves of MnO2 calcined at 200, 400 and 600°C, respectively. and
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59 (d) is Cs vs. scan rate of MnO2-based electrodes produced with MnO2 calcined at different
60 temperatures.

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3 Table 1. Cs of electrodes at different scan rates.
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5 Specific Capacitance (F/g)
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7 Scan Rates (mVs-1)
8 Samples

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9 1 5 10 50
10 MnO2-(200 ˚C) 177 92 50 19
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12 MnO2-(400 ˚C) 170 91 47 17
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MnO2-(600 ˚C) 110 78 33 11

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17 4.2.2 Effect of calcination temperature
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19 CV curves of electrodes produced with MnO2 calcined at various temperatures are shown in
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Fig. 6. The amorphous MnO2-(calcined at 200 ˚C) showed higher Cs of about 177 F/g while

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22 the MnO2-(calcined at 400 ˚C) and MnO2-(calcined at 600 ˚C) showed Cs of 170 F/g and 110
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24 F/g at a scan rate of 1 mVs-1, respectively. This may be due to higher surface area and pore size
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26 offered by the amorphous MnO2 [30]. Certainly, increasing temperature increases crystallinity
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of MnO2 as a result Cs of MnO2 electrodes decreased [49]. MnO2-(200 ˚C) and MnO2-(400
˚C) showed a near rectangular quasi state CV curve while the crystalline
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56 Fig. 6. CV curves of MnO2-based electrodes having different morphologies at 1 mVs-1.
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58 MnO2 nanowires showed a small reversible reduction peak at +0.35 V. Amorphous MnO2
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60 favors EDLC behavior more than pseudo-capacitive behavior due to larger surface area while

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3 crystalline MnO2 has mixed effect. No noticeable oxidation peaks can be seen in CV curve of
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5 amorphous MnO2 owing to the limited potential window for CV analysis.
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MnO2 stores charge according to the reaction (Eq. 8) [47, 50]:
8

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10 𝑀𝑛𝑂2 + 𝐾 + + 𝑒 ←→ 𝑀𝑛(𝑂𝑂)− 𝐾 + (8)
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12 K+ ions are stored in MnO2 through a reversible redox reaction in which K+ forms and
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intermediate compound Mn(OO)- K+ with MnO2. This reaction is reversible, and it can store

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4.3 Galvanostatic charge discharge
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GCD test was carried out on all three MnO2-based electrodes produced with MnO2 of different
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23 between 0-0.45 V potential window like the CV curves.
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25 Table 2. Cs calculated from GCD.
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MnO2
calcined at
an
Specific Capacitance (F/g)
1 A/g 3 A/g 5 A/g 10 A/g
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32 200°C 173 162 150 99
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34 400°C 148 134 126 87
35 600°C 79 68 56 41
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The charging and discharging currents were set depending on the mass loading, which in this
41 case was approximately 3 mg/cm2. MnO2-(200 ˚C) showed better Cs values compared to the other
42
43 calcined MnO2 powders as shown in Table 2. Increasing the current density decreases the Cs by
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45 reducing the time for charging and discharging cycles. The discharging times for MnO2 calcined
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at 200, 400 and 600 °C were 78, 67 and 36 seconds, respectively. The charging slope is increasing
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48 while the discharging has a decreasing slope as illustrated in Fig. 7 which showed pseudo-
49
50 capacitive behavior and some irreversibility of MnO2 [30]. Current density has inverse relation
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45 Fig. 7 (a), (b), (c) are GCD cycles of MnO2 calcined at 200 ˚C, 400 ˚C and 600 ˚C,
46 respectively. While (d) is comparative GCD graph at 1 A/g.
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49 4.4 EIS analysis
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51 Nyquist plots of MnO2 calcined at different temperatures are shown in Fig. 8. The semi-circular
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52 part of the curves represents the impedance of electrodes while the increasing straight line is
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54 the Warburg impedance represented by Zw and is the resistance offered due to cation diffusion.
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56 The electrical equivalent circuit (EEC) model (inset shown in Fig. 8) was fitted to EIS data to
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understand the electrochemical behaviour of different morphologies of MnO2. In this EEC
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59 model Rs represents the solution resistance, Cdl is the EDLC, Rct is the charge transfer resistance
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3 while Cpe1 is the constant phase element. Basically, all curves obtained showed similar
4
5 characteristics, the semicircle section of the curves is also approximately the same. The internal
6
7 resistance of each electrode was in the range of 0.5±0.1 ohm as determined by the EEC model.
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The parameters calculated from EEC model fitting are shown in Table 3. The Rct values for

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10 MnO2 calcined at 200, 400 and 600 °C are 1.605, 0.515 and 0.636 Ω, respectively.
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Fig. 8. Nyquist plots of MnO2 calcined at various temperatures with EEC model.
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The lower Rct values favours pseudo-capacitance phenomenon and improves the
46
47 electrochemical properties [51]. The Cdl values for each electrode are 0.385, 0.168 and 0.056
48
49 F. The higher the value of Cdl the more the charge is stored electrostatically on the MnO2
50
51 surface favouring EDLC behaviour. It could be concluded that MnO2 calcined at 200 °C was
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52 amorphous and stored charge through both mechanisms (EDLC and pseudo-capacitive) while
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54 MnO2 calcined at 600 °C is crystalline and stores charge through only pseudo-capacitive
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56 mechanism. MnO2 calcined at 400 °C gave mixed properties as it had an intermediate structure.
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3 Table 3. EIS values calculated from EEC model fitting.
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5 Components in Samples
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7 equivalent circuit MnO2 200°C MnO2 400°C MnO2 600°C
8

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9 Rs (Ω) 0.421 0.598 0.340
10 Rct (Ω) 1.605 0.515 0.636
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12 Cdl (F) 0.385 0.168 0.056
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Goodness of Fit 0.00152 0.00426 0.01991

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17 The percentage charge retention of various electrodes was calculated from CV curves which
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19 are presented in Fig 9. The highest charge retention of 99.2 % at a scan rate of 50 mVs-1 was
20
obtained for MnO2 calcined at 600 °C. Identical CV curves in Fig. 9 (inset) showed excellent

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22 cyclic stability of MnO2 electrodes after 1000 cycles of charge and discharge.
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24
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26 Table 4. Cs at different no. of cycles.
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an %-age Charge Retention

30 MnO2-(200°C) MnO2-(400°C) MnO2-

31 No. of cycles
32 (600°C)
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35 1st 100.00 100.00 100.00
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37 200th 93.80 92.70 98.40
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400th 91.60 89.20 98.50
40 600th 90.30 86.70 98.90
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42 800th 89.70 84.70 99.00
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44 1000th 89.10 83.30 99.20

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Fig. 9 Charge
24 retention at 50
25 mV/s for 1000
26 cycles of
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produced with
MnO2 calcined
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at (a) 200 ˚C
32 (b) 400 ˚C and
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33 (c) 600 ˚C.
34 Inset shows
35 CV curves
36 obtained at
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various cycles.
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3 Table 5. Energy and power densities for different MnO2-based electrodes
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6 Electrodes produced with Energy Density Power density
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MnO2 calcined at different Wh/kg W/kg
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9 temperatures
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11 (°C)
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13 200 4.86 224.3

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400 4.16 223.5
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16 600 2.22 222.0
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20 Energy densities and power densities of electrodes produced with MnO2 calcined at different

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temperatures are shown in Table 5. Electrodes produced with MnO2 calcined at 200 and 400
23 °C gave almost the same energy densities and power densities compared to that calcined at 600
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25 °C. Energy and power density is more important for batteries compared to supercapacitors
26
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29
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(SCs) due to low operating voltages of SCs. The present work provided a potential window of
0.45 V, which had a really big impact on these values. Energy density value is proportional to
30 the square of potential window (V) [46].
31
32 A comparison between present work and already published research work is given in Table 6.
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34 Table 6. Comparison of MnO2 -based electrodes developed in this work with published
35 research.
36
37 Specific Current Capacitance
38 Research
39
Method Electrolyte Capacitance Density Retention Ref.
Group
40 F/g A/g %
41
42 Air
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44 Present work Calcination 3M KOH 177 1 89 -

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46
(200 oC)
47 Weidong Hydrothermal
48 1M Na2SO4 110 1 92 [52]
49 et al. (150 oC)
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51 Wang Hydrothermal 0.5M
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52 118 1 91 [53]
et al. (150 oC) Na2SO4
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54 Sankar
55 Sonochemical 1M Na2SO4 136 0.5 72 [44]
56 et al.
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58 Subramanian Hydrothermal
59 1M Na2SO4 160 0.2 83 [54]
et al. (140 oC)
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5 Table 6 shows comparison of this research with the published literature. Previous studies
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7 reported use of Na2SO4 as electrolyte, but we found it to be corrosive to Ni foam as it damaged
8
electrodes when electrodes were immersed for longer time. Therefore, in present study Na2SO4

pt
9
10 was replaced with KOH as electrolyte. Electrodes which were developed with MnO2 calcined
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12 at 200 °C (present work) gave higher Cs and comparable charge retention than some of the
13

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14 MnO2 electrodes already reported (Table 6).
15
5. Conclusions
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17 MnO2 was successfully synthesized by reduction of KMnO4 and air calcination. MnO2 calcined
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19 at 200, 400 and 600 oC had flake, mixed flake and nanowires and nanowires-like morphology
20
as determined by SEM. XRD analysis showed that MnO2 formed at 200 oC was amorphous

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22 and crystallinity of MnO2 increased with increasing calcination temperature. Calcination at 600
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24 C resulted in formation of crystalline α-MnO2. CV revealed that MnO2 with amorphous
o
25
26 morphology (calcined at 200 °C) showed more EDLC behaviour than pseudo-capacitive, semi-
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crystalline MnO2 (calcined at 400 °C) showed intermediate charge storage mechanism and
crystalline MnO2 (calcined at 600 °C) showed purely pseudo-capacitive behaviour. Electrodes
30
31 developed with MnO2 calcined at 200, 400 and 600 °C showed maximum Cs of 177, 170 and
32
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33 110 F/g at a scan rate of 1 mVs-1, respectively. EIS analysis also showed more charge storage
34
by MnO2 calcined at 200 oC compared to those calcined at 400 and 600 oC. GCD analysis
35
36 showed that MnO2-(200 °C) electrode showed 89 % capacitance retention and showed
37
38 excellent cyclic stability
39
40 Acknowledgment
41 The authors would like to thank higher education commission (HEC) of Pakistan for providing
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financial support to carry out this research work.

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