Maheswari 2015

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Article
Supercapacitor Behaviour of Cerium Oxide
Nanoparticles in Neutral Aqueous Electrolytes
Nallappan Maheswari, and Gopalan Muralidharan
Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.5b02144 • Publication Date (Web): 01 Dec 2015
Downloaded from http://pubs.acs.org on December 4, 2015
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Page 1 of 24 Energy & Fuels
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4 Supercapacitor Behaviour of Cerium Oxide Nanoparticles in
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6 Neutral Aqueous Electrolytes
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9 Nallappan Maheswari and Gopalan Muralidharan *
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11 Department of Physics, Gandhigram Rural Institute - Deemed University, Dindigul, Tamilnadu, India
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13 *Corresponding author e-mail: muraligru@gmail.com
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Energy & Fuels Page 2 of 24
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ABSTRACT: Hexagonal CeO2 nanoparticles have been prepared through hydrothermal method
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6 using CTAB (Cetyl trimethyl ammonium bromide) as the surfactant. The structural and
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8 morphological studies have been made using XRD, FTIR, SEM and TEM analysis. The
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electrochemical behaviour of CeO2 nanoparticles was investigated using cyclicvotammetry (CV),
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13 charge- discharge studies (CHDH) and ac impedance spectroscopy in different neutral
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15 electrolytes such as NaCl, KCl, Na2SO4 and K2SO4. Maximum Specicific capacitance of 523 F
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18 g-1 was attained with the NaCl electrolyte at 2 mV s-1. The capacitance values obtained with
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20 various electrolytes are in the order of NaCl > Na2SO4 > KCl > K2SO4. Charge- discharge and
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22 impedance analysis further confirms this behaviour. After 2000 cycles of charging and
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25 discharging only 18% degradation in the specific capacitance could be observed. All the
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27 electrochemical studies indicate the NaCl aqueous electrolyte to be most suited electrolyte for
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CeO2 supercapacitor electrodes.
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36 Keywords: Neutral aqueous electrolytes, hexagonal CeO2, Hydrothermal method, Cyclic
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38 stability, Hydration number
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1. INTRODUCTION
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7 With the fear that the fossil fuels may not last another couple of decades, the need to
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9 develop environmentally friendly, non polluting, renewable energy systems and energy storage
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11 devices is the order of the day.1 As energy storage devices, supercapacitors have drawn
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14 increasing attention in addressing the emerging energy demands on account of their trademark
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16 features like high power delivery, long cycle life, and fast charge /discharge characteristics.2, 3
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Supercapacitors can be divided into two categories according to the energy storage principle,
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21 namely, electrochemical double layer capacitors (EDLC’s) and psuedocapacitors.4 The former is
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23 usually made of mesoscopic materials like activated carbon, carbon nanotube, graphene that are
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26 associated with high specific surface area. Separation of charges at the interface between the
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28 electrode and the electrolyte is the mechanism of charge storage in EDLCs. Transition metal
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30 oxides with several oxidation states and conducting polymers permit insertion and de-insertion of
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33 charges through redox reactions. These are labeled as pseudocapacitor materials.5, 6, 7 In contrast
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35 to EDLCs, pseudocapacitors exhibit larger specific capacitance owing to their redox properties. 8
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37 RuO2 is accepted as the best electrode material for supercapacitors. Its commercial exploitation
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40 is hindered by the fact that it is a costly material while its limited availability on the earth’s crust
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42 makes it worse. As an alternative to ruthenium oxide MnO2,10 NiO,11 Co3O412 have been
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extensively studied as pseudocapacitor electrode material. Recently new types of electrode
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47 materials have been explored to further enhance the energy density of these pseudocapacitors.
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49 Due to 4f electronic structure, rare earth elements exhibit unique spectroscopic properties. In
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52 particular, CeO2 has been seen as a potential electrode material for supercapacitors due to the
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54 following reasons: abundance, excellent redox properties.13, 14 From the literature, it can be seen
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56 that there are only few reports on the supercapacitor behaviour of the rare earth oxides.
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Proper selection of electrode materials and electrolytes is one of the means to achieve greater
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6 charge storage capacities associated with large energy densities. Non aqueous organic
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8 electrolytes with higher decomposition voltage have been identified for use in a larger
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electrochemical window. The high cell voltage of supercapacitors using organic electrolytes
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13 allows them to deliver a higher specific energy than with aqueous electrolytes, but it suffers from
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15 the fact that these are flammable, high cost, low ionic conductivity and exhibit bulging on
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18 continuous cycles of charge- discharge.15 Aqueous electrolytes that are capable of higher ionic
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20 conductivity deliver higher power densities. The added advantage of the aqueous electrolytes is
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22 that they are environment friendly. The non-aqueous electrolytes require an anhydrous
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25 atmosphere for cell assembly while this difficulty is circumvented with the aqueous
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27 electrolytes.16 The high mobility of protons due to its smaller size and weight, and the associated
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high ionic conductivity makes aqueous acidic electrolytes an attractive option. In addition to the
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32 degradation of the electrode material, corrosion of current collectors and environmental concerns
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34 need to be considered with strong acid electrolytes.17 Large number of research groups are
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37 putting efforts at identifying safe, environment friendly power sources towards use in flexible,
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39 wearable devices.18 These issues have created interest in the use of neutral electrolytes.
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41 Generally a neutral electrolyte exhibits low H+ and OH- concentration, resulting in the use of a
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44 higher potential window without gas evolution.16, 19
For the first time we have examined the
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46 supercapacitive properties of hydrothermally synthesized cerium oxide nanoparticle in different
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48 neutral aqueous electrolytes such as KCl, NaCl, K2SO4, Na2SO4. To the best our knowledge,
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51 very little literature is available on the optimization of an electrolyte for CeO2 nanoparticles with
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53 respect to their electrochemical behaviour. The pseudocapacitive performance of CeO2 electrode
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with these electrolytes has been investigated and reported in this paper.
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6 2. MATERIALS AND ELECTRODE PREPARATION
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8 2.1. Materials and methods
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Analytical grade reagents have been employed in the present work. 0.2 M of Ce(NO3)3.
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13 6H2O was dissolved in 40 mL of water. Appropriate amount of CTAB (Cetyl trimethyl
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15 ammonium bromide) was added to get 0.05 M of CTAB in the solution. The pH of the solution
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18 was maintained at 10 by the drop wise addition of 1 M NaOH. This solution was subjected to
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20 continuous stirring for 2 h. The hydrothermal reaction of this solution was achieved by placing
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22 this solution at 160 ̊C in a Teflon-lined stainless steel autoclave for 24 h. The autoclave was
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25 allowed to cool to room temperature. The precipitate formed in this process was washed with
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27 deionized water and ethanol several times. The final product was dried in an atmosphere of air
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at 80 ̊C for 24 h and then calcined at 500 ̊C for 4 h in air. The X-ray diffraction patterns of the
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32 samples were recorded using a PANalytical XPERT-PRO X-ray diffractometer with Cu Kα
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34 radiation. FTIR Spectra have been recorded using a Perkin-Elmer Spectrum BX-II
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37 spectrophotometer. The surface morphology of the CeO2 was studied using Tescan VEGA-3
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39 LMU Instrument. Transmission electron microscopy (TEM) images were obtained with JEOL
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41 JEM 2100 (200 kV) system to study the morphology of the samples.
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2.2. Electrode preparation and electrochemical measurements
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47 CHI-660D electrochemical workstation was used to make electrochemical measurements.
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49 80 % CeO2 as the active material, 15 % of activated carbon and 5 % PTFE as the binder were
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52 used to make the working electrode. Few drops of ethanol were used as the solvent to aid the
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54 formation of slurry. Pretreated graphite sheet (1cm x 1cm) was used as the current collector. 1
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56 mg of the active material was used to prepare the working electrode. The drying of the prepared
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electrode was carried out in an atmosphere of at 70 ̊C for 12 h. The electrode prepared
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6 employing this methodology was used as the working electrode. 1 M aqueous solutions of KCl,
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8 NaCl, Na2SO4 and K2SO4 were used as the electrolyte. The three electrode cell configuration
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was employed for all the electrochemical measurements. Here, the working electrode was made
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13 up of CeO2 prepared in the present work, a platinum wire as the counter electrode and Ag/AgCl
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15 as the reference electrode. A potential window of 0 to 0.8 V was chosen for the
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18 cyclicvoltammetry measurements. Scan rates of 2 mV s-1 to 100 mV s-1 were employed in
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20 making CV measurements. The same potential window of 0 to 0.8 V was used in carrying out
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22 charge-discharge characterization at different current densities. AC amplitude of 5 mV and bias
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25 potential of 0.3 V were applied to the electrodes in making electrochemical impedance
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27 measurements. The EIS data were obtained in the frequency range of 0.01 Hz and 100 kHz.
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RESULTS AND DISCUSSION
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32 3.1. Structural and morphological analysis
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34 X-ray diffraction pattern of CeO2 nanoparticles is presented in figure 1. The diffraction
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37 peaks could be associated with (111), (200), (220), (311), (400), (331) planes of cubic CeO2.
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39 The XRD patterns agree well with the JCPDS card (81-0792) indicating the cubic phase of CeO2.
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41 The average crystallite size of 11.7 nm could be obtained through Debye-Scherrer formula.
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22 Figure 1. XRD pattern of CeO2 nanoparticles
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25 The FTIR spectrum of CeO2 is shown in figure 2. The C–H stretching mode of
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28 hydrocarbons attached to CTAB could be identified through absorption band in the region 2800–
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30 2900 cm−1. The absorption band at 1026 cm−1 is assigned to the stretching mode of C=O
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33 vibration.20, 21
The Ce–O stretching band around 450 cm−1 reveals the formation of CeO2
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35 nanoparticles.22, 23 OH related vibrations were found through the bands around 3400 and 1625
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Figure 2. FTIR spectrum of CeO2 nanoparticles
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The SEM micrographs of the CeO2 nanoparticles are shown in figure 3(a, b). It reveals
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6 the uniform distribution of CeO2 nanoparticles.
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52 Figure 3. SEM ( a,b) and TEM (c-f) images of CeO2 nanoparticles
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The TEM images of the CeO2 nanoparticles (figure 3c-f) reveal the hexagonal
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6 morphology of the nanoparticles. The well distributed particles can shorten the diffusion path
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found to be 14 nm. This agrees well with the crystallite size obtained from the XRD pattern.
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14 Scheme 1 represents the formation mechanism of CeO2 hexagonal nanostructures.
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16 CTAB controls the hydrolysis rate during nucleation process and ensures the slow release of OH-
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to form Ce(OH)4-. During the protracted hydrothermal treatment, the Ce(OH)4- converted to
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21 CeO2.25 After calcining at 500 ̊C the small size hexagonal nanostructure were obtained.
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Scheme 1. Schematic representation of CeO2 nanoparticle formation
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3.2. Electrochemical Studies
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55 The cyclic voltammetry traces of CeO2 electrode in different electrolytes (NaCl, KCl,
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57 Na2SO4 and K2SO4) corresponding to various sweep rates are shown in figure 4a-d. In all the
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electrolytes CeO2 electrodes exhibit pseudocapacitance nature, no obvious redox peaks could be
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6 observed. The mechanism proposed for charge storage of CeO2 based electrodes are the
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8 intercalation of the monovalent alkali cations (Na+, K+). The chemical equation for the same is
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given by
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14 CeO2 + M+ + e- CeOOM
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17 Where M= Na+, K+. It should be noticed that the proposed mechanism involved a redox reaction
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19 between the III and IV oxidation states of CeO2.26 From the CV curves, specific capacitance was
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22 estimated using the formula cited elsewhere.27
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24 The maximum specific capacitance of 523±5, 488±5, 502±5, 222±2 F g-1 were obtained
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with NaCl, KCl, Na2SO4, K2SO4 electrolytes respectively, at the lowest scan rate of 2 mV s-1.
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40 Figure 4. CV curves of CeO2 nanoparticles with different electrolytes at different scan rates (a) NaCl
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46 The shape of the CV curve indicates the capacitive behaviour. It is well known that the
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48 voltammetric current is always directly proportional to scan rate.28 At lower scan rates, the
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electrolyte ions completely diffuse into the material and hence they have enough time to utilize
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53 all the active sites of the electrode material for charge storage. At higher sweep rates, the
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55 movement of electrolyte ions is limited by time constraints. Only the outer active surface is
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utilized for charge storage.29 From figure 4e, it can be seen that the supercapacitor behaviour is
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of the trend NaCl > Na2SO4 > KCl > K2SO4. This can be ascribed to the size difference among
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6 the hydrated electrolyte ions and transference numbers of anion and cation in the electrolytes.
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8 Generally K+ ions have a small hydration sphere.30 But compared with NaCl , both Na+ and K+
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ions have similar hydration numbers, but ionic radius of Na+ (0.95 Å) is far lower than K+ (1.33
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13 Å) ion which permits better diffusion of Na+ ions and it leads to a larger capacitance (7 %)
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15 with the NaCl electrolyte. Compared to Na2SO4, NaCl electrolyte provides larger specific
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18 capacitance (4 %). The SO42- counterions of Na2SO4 (258 pm) are bigger than Cl- (190 pm)
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20 counterions of NaCl. The size difference is the most probable cause for the decrease in the
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22 capacitance values with sodium sulphate.32 Similar results were obtained by Jeiong et al.32 for
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25 MnO2 nanostructures and Reddy et al.33 for MnO2 prepared through sol-gel method. They
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27 reported the highest capacitance with NaCl electrolyte than KCl and Na2SO4 electrolytes. The
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observed specific capacitance values are nearly twice that of the values reported in the literature,
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32 289 F g-1 (5 mV s-1 in 0.5 M Na2SO4) reported by Kalubarme et al.11 while Wang et al.34 reported
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34 208 F g-1 for CeO2 / graphene electrode in a potential window 0.6 V (in 3 M KOH). The poor
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37 crystallinity and smaller hexagonal nanoparticles are found to enhance the mobility of the charge
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39 carriers and increase the capacitance.
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41 The galvanostatic charge- discharge measurements of CeO2 electrode carried out in the
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44 four electrolytes at current densities of 2, 5, 10 A g-1 are depicted in figure 5. The symmetric
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46 structure of the charge- discharge curves indicates excellent electrochemical reversibility of
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48 CeO2 electrode. The specific capacitance of the electrodes was calculated using the charge-
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51 discharge data using the equation mentioned elsewhere.27
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40 The maximum capacitance was obtained at a current density of 2 A g-1. The specific
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capcacitance values in different electrolytes are: 457±5 (NaCl), 395±4 (KCl), 400±4 (Na2SO4),
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45 and 320±3 F g-1 (K2SO4). These values agree very well with those obtained through CV.
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47 Maximum specific capacitance of 644 F g-1 was reported by Padmanathan et al.25 They used 3 M
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KOH as the electrolyte while the current density was maintained at 0.5 A g-1. It is to be noted
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52 that the present results are obtained with neutral electrolytes and at four times the current density
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54 employed by Padmanathan and his co-workers. Scheme 2 explains the electrochemical
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57 mechanism of CeO2 electrode. Hexagonal nanostructures act as an ion buffering reservoir and
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hence enhance the Na+ diffusion rate within the bulk of the material. The nanosized hexagonal
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Scheme 2. Schematic representation of the electrochemical performance of CeO2
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electrode
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Conductivity and mobility of the cations are important factors that determine the
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38 behaviour of the electrolytes. The hydration radius of Na+ is larger than that of K+. Hence Na+
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40 ions have a larger hydration sphere than K+ ions as a result of the strong interaction between
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Naδ+ and H2Oδ-. But, it is interesting to note that the overall radius of hydration for all ions is
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45 about the same, from 3.3 to 3.8 Å.32, 33 Jeiong et al.32 and Reddy et al.33 reported that the size of
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47 the hydration sphere is not a major deciding factor. In the case of KCl and NaCl the Na+ yields
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50 higher specific capacitance inspite of the fact that the potassium ions exhibit better conductivity.
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52 Jeiong et al.32 and Reddy et al.33 reported similar results with MnO2 nanostructures. The values
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54 of discharge capacitance and available active sites against current density are presented in Figure
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6a–d. The available active sites (Z) are determined from the specific capacitance of the CeO2
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6 electrode using the following equation 35
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12 Where Cs is the specific capacitance, ∆V , the potential window, W , the molecular
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15 weight of CeO2 (172.115 g) and F , the Faradic constant.
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50 Figure 6. Specific capacitance and active site against current density in (a) NaCl (b) KCl, (c) Na2SO4 and
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Figure 6 testifies that the electrode is endowed with higher number of active sites and
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6 higher specific capacitance at low-current density irrespective of the kind of electrolyte
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8 employed. It is reasoned that the number of active sites accessed by the ions is quite high at low
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current densities due to large amounts of time available for diffusion. The reduction in the
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13 access to inner sites of the electrode leads to a reduced capacitance at higher rates of charge –
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15 discharge.36
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18 Electrochemical impedance spectroscopy (EIS) studies were carried out for the
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20 CeO2 electrode with the four (1 M NaCl, KCl, Na2SO4 and K2SO4) at conditions mentioned in
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22 section 2.2. These measurements are carried out as the charge transfer resistance and the
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25 solution resistances are essential parameters that characterize the performance of a
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27 supercapacitor The typical Nyquist plots of CeO2 electrode are shown in Figure 7a. The solution
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resistance (Rs) is obtained from the intersection of the high frequency side with the horizontal
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32 axis of the Nyquist plot. The semicircle observed at high-to-medium frequency range yields the
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34 charge transfer resistance (Rct) associated with the CeO2 electrode. A spike associated with the
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37 low-frequency region is indicative of the ideal capacitive behaviour of the electrode. Warburg
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39 impedance (ZW) of the electrode, i.e., the diffusive resistance of ions Na+ and K+ into electrode is
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41 obtained through this spike.36, 37 Of the four electrolytes employed in the present study, NaCl
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44 (0.84 Ω) is the one that is endowed with the lowest charge transfer resistance. The other
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46 electrolytes exhibited considerably larger resistance: Na2SO4 (0.9 Ω), KCl (1.1 Ω) and K2SO4
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48 (1.4 Ω). Table 1. Shows the impedance data fitted to an equivalent circuit. All the impedance
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51 values suggest that NaCl is the most suitable electrolyte for CeO2 electrode.
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Table 1. The components of the equivalent circuits obtained by fitting the impedance data.
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37 Electrolytes Rct (Ω) Cdl (mF) Rs (Ω) ZW Cp(F)
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39 NaCl 0.84 0.795 2.55 0.0816 0.9732
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42 KCl 1.1 0.420 4.22 0.0795 0.9437
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44 Na2SO4 0.9 0.584 3.30 0.0795 0.9521
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K2SO4 1.4 0.335 4.32 0.0713 0.8336
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51 Table 1. shows the parameters obtained by fitting the impedance data to an equivalent
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54 circuit. The fitted equivalent circuit model is shown in Figure 7b. The model circuit comprised
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electrode/ electrolyte boundary. Cp is the pseudocapacitance component and Rct is the either
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6 resistance associated with the transfer of charges at the boundary of the electrolyte and electrode.
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8 The Rct values are around 0.84- 1.4 Ω for all the electrolytes. ZW is the semi infinite diffusion of
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cations in the electrode. The Warburg impedance values for CeO2 electrode in various
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13 electrolytes due to electrolytes’ cation diffusion within the electrode. The higher Warburg
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15 impedance in the case of NaCl electrolyte compared to other electrolytes may be attributed to the
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18 more affordable diffusion of electrolyte cations (Na+) in the electrode.38 The observed higher
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20 capacitance in NaCl electrolyte associated with the decrease in charge transfer resistance and an
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22 increase in Warburg impedance.
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25 Cyclic stability is another important aspect of a supercapacitor operation. Figure 8
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27 shows the effect of continuous cycles of charge-discharge on the specific capacitance and
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Columbic efficiency of the prepared electrode in 1M NaCl. From the cyclic test on CeO2
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32 electrode, it is noted that even after 2000 continuous charge discharge cycles, the electrode could
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34 retain 82 % of the initial value. It is essential to note that the cyclic stability test has been
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37 conducted at a far larger current density of 10 A g-1. Figure 8 illustrates the excellent long term
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39 cyclic stability of the CeO2 electrode after 2000 cycles. The Columbic efficiency was calculated
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41 from the relation 27
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45 td
46 η= ×100% (4)
47 tc
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Where η is the Columbic efficiency; t d is the discharging time and t c is the charging time. Even
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52 after 2000 cycles, 100 % of Columbic efficiency could be observed.
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60 18
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Figure 8. Cyclic stability and Columbic efficiency of CeO2 electrode in NaCl electrolyte at a current
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24 density of 10 A g-1
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27 This is an indication of excellent kinetic reversibility associated with the hexagonal
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29 nanoparticles of cerium oxide. The overall electrochemical studies strongly suggest that I M
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NaCl electrolyte is the most suited electrolyte for working with CeO2 electrodes prepared via
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34 hydrothermal method using CTAB.
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36 4. CONCLUSION
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39 The CeO2 nanoparticles have been prepared by hydrothermal method. XRD pattern
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41 reveals the cubic phases of CeO2. FTIR spectrum confirms the presence of CeO2. The
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43 performances of electrochemical studies on CeO2 electrode were investigated with various
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46 aqueous electrolytes such as NaCl, KCl, Na2SO4 and K2SO4. The CeO2 electrode yielded the
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48 maximum specific capacitance in NaCl electrolyte. The measurements of the same from
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cyclicvoltammetry, charge- discharge analysis and impedance spectroscopy confirm the aqueous
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53 NaCl to be best candidate. The cyclic test on CeO2 electrode showed the good capacity
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55 rentention about 82 % over 2000 cycles. All the electrochemical studies suggest that NaCl is the
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best suited electrolyte for supercapacitor applications employing cerium oxide.
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6 AUTHOR INFORMATION
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8 Corresponding Author
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E.mail: muraligru@gmail.com
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13 Phone: +91 451 2452371. Fax: +91 451 2454466
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