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Silicon Carbide Nano-Cauliflowers for Symmetric Supercapacitor Devices Amit Sanger, Ashwani Kumar, Arvind Kumar, Pawan Kumar Jain, Yogendra Kumar Mishra, and Ramesh Chandra Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.6b02243 • Publication Date (Web): 16 Aug 2016 Downloaded from http://pubs.acs.org on August 16, 2016

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Industrial & Engineering Chemistry Research

Silicon

Carbide

Nano-Cauliflowers

for

Symmetric Supercapacitor Devices Amit Sanger1, Ashwani Kumar1, Arvind Kumar1, Pawan Kumar Jain2, Yogendra Kumar Mishra3,*, Ramesh Chandra1,* 1

Nanoscience Laboratory, Institute Instrumentation Centre, Indian Institute of Technology

Roorkee, Roorkee - 247667, India 2

Center for Carbon Materials, International Advanced Research Centre for Powder Metallurgy

and New Materials (ARCI), Hyderabad - 500005, India 3

Functional Nanomaterials, Institute for Materials Science, Kiel University, Kaiserstr. 2, D-

24143 Kiel, Germany ABSTRACT The efficiency of silicon carbide (SiC) nano-cauliflowers (NCs) as electrode material for supercapacitor application has been investigated in detail in present work. The SiC NCs were deposited on Ag coated porous alumina (AAO) substrates via DC magnetron cosputtering technique at room temperature. The Ag coated porous AAO substrate acts as excellent current collector and also enhances the high specific capacitance of SiC NCs upto ~ 300 F/g at 5 mV/s. The fabricated symmetric supercapacitor device delivered a high specific capacitance (188 F/g at 5 mV/s), good cycling ability (97.05% capacitance retention after 30,000 cycles), high energy

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density (31.43 Wh/kg), and also a high power density (~18.8 kW/kg at 17.76 Wh/kg) in a voltage range of 1.8 V. These observed excellent electrochemical performances of the present SiC NCs based device, suggest it’s tremendous potential as supercapacitor electrodes in energy storage applications. Keywords: Silicon carbide nano-cauliflowers, supercapacitor, porous AAO, sputtering. 1. Introduction In last couple of years, the energy sector has been the prime focus in terms of introducing several alternative energy resources, and developments in the direction of supercapacitors (SCs) seem to have very promising future because of their high storage capacities alongwith utilization simplicities1-5. Unlike batteries, SCs store charge electrostatically on the surface of active material rather than as a chemical state6. Based on charge storage mechanism, SCs can be charged quickly for millions of charge -discharge cycles, leading to high power density. The problem with SCs is their low energy density, i.e. energy stored per unit active material weight is very small7. However, the utilized material in the supercapacitor exhibits very prominent role because it’s properties mainly decide the performance of supercapacitors8. Recent study of SCs active materials has focused on porous carbonaceous materials such as carbon nanotubes, porous carbon, and graphene, in order to achieve high specific capacitance and, hence, energy density915

. These carbonaceous nanomaterials, however, oxidize at high temperatures in the presence of

oxygen16. On the other hand, SiC has attracted much attention as promising electrode material for energy storage applications due to its high thermal and chemical stability in many harsh physicochemical environments, including high temperature oxidizing environment, long life time 2 ACS Paragon Plus Environment

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and high temperature operations17-19. Sarno et al., adopted activated carbon-derived SiC nanoparticles based electrodes with the specific capacitance of 114.7 F/g at 0.12 A/g20. Zhuang et al., fabricated SiC film through CVD route17. The electrode showed the areal capacitance of 72.7 F/cm2 at 100 mV/s. To further improve the performance of SCs, Alper et al., examined CVD fabricated SiC nanowires based electrodes and showed areal capacitance of 240 µF/cm2 at 100 mV/s21. However, only the surface of active material can efficiently contribute to the total capacitance while the most of the material below the surface could hardly take part in the electrochemical process, leading to lower than expected values of specific capacitance22. The chemical synthesis methods always involve toxic reagents, solvents, etc. and hence some byproducts more likely always remain which limit the overall accessibility of nanoscale features22-24. Therefore, it is still a great challenge to improve the electrochemical utilization of active materials by fabricating electrodes with novel nanostructures. Hence, their versatile fabrications using appropriate techniques and in desired manner have always been in the main focus. An alternative concept is to directly grow integrated array of nanostructures on current collector as binder-free electrodes for supercapacitors. In contrast, the physical vapour deposition (PVD) methods provide an eco-friendly route to fabricate surface clean SiC hierarchical nanostructured materials25-26. Based on the above considerations, here we report the fabrication of SiC NCs working electrode using DC magnetron cosputtering. The electrochemical characteristics of the as-prepared SiC NCs as an electrode material for supercapacitors have been investigated on the basis of cyclic voltammetry (CV), galvanostatic charge/discharge (GCD) cycles, and electrochemical impedance spectroscopy (EIS) and the results are discussed in detail. 2. METHODS 3 ACS Paragon Plus Environment


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2.1. Materials and Chemicals Silicon (Si), carbon (graphite, C) and silver (Ag) targets (2” diameter) of high purity (99.99%) were purchased from Testbourne Ltd., UK. Argon (Ar) gas cylinder of high purity (99.9%) was purchased from Sigma Gases, India. Oxalic acid (H2C2O4), sodium sulfate (Na2SO4) and aluminium foil (0.3 mm thick) were obtained from Merck, India. Deionized water was used for electrochemical anodization. 2.2. Preparation of current collector Synthesis of porous alumina was already discussed in authors’ previous study27 (Figure 1). Unfortunately, the AAO template cannot be used as supercapacitor electrode because it is an insulator. However, the structural features of the AAO membrane provide a hint for the design of nanostructured electrode for supercapacitors. Subsequently deionized water rinsed porous AAO substrate was kept in the sputtering chamber at a distance of 5 cm from the Ag target. The sputtering chamber was initially evacuated to a base pressure of 2×10−6 Torr. Thereafter working pressure of sputtering chamber was kept constant at 10 mTorr by constant flow of Ar gas using mass flow controller (MKS). The deposition of Ag was carried out for a period of 5 sec by applying 30W sputtering power at room temperature. The resistance of Ag coated porous AAO current collector was found to be ~1 Ω, i.e., good for supercapacitor application. 2.3. Preparation of working electrode and symmetric supercapacitor device The working electrode was prepared with deposition of SiC NCs directly on the current collector by DC cosputtering technique (Figure 2). The distance between targets (Si and C) and current collector was kept at 6 cm. Prior to deposition, the sputtering chamber was initially evacuated to


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a base pressure of 2×10−6 Torr. The working pressure was kept constant at 10 mTorr by constant flow of Ar (20 sccm) gas using mass flow controller. The deposition of SiC NCs was carried out for a period of 1 hour at room temperature by applying 80W and 85W sputtering power for Si and C, respectively. The working electrodes with an exposed area 1×1 cm2 was used in three electrode system cell. The loading mass of SiC was about 1.4 mg/cm2. The loading mass was calculated by taking difference between measured weight of the working electrode and current collector. The details are given in supplementary information. The symmetric supercapacitors were assembled by using two working electrodes of area 1×1 cm2 with an electrode gap of 0.26 mm controlled by a separator (Whatman, Grade GF/C) and 1M Na2SO4 aqueous electrolyte. 2.4. Characterizations XRD patterns of working electrode were recorded using Bruker AXS-D8 Advance diffractometer. The morphologies and chemical composition of the samples were characterized by FE-SEM (Carl Zeiss, Ultra plus), EDAX (Oxford Instruments) and Raman spectroscopy (Renishaw, United Kingdom). CV curves were measured in a voltage range of 0-1.8 V at different scan rates using an electrochemical work station (CHI 660D). The GCD cycles were measured within a voltage range of 0-1.8 V at different current densities to evaluate the specific capacitance (Cs). Thirty thousand cycles were performed to measure the capacitance retention over GCD curves. EIS was measured from 10 mHz to 100 kHz. The details for calculations are given in supplementary information. 3. Results and Discussion 3.1 Structural properties



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As shown in Figure 3a, XRD analysis of working electrode depicts amorphous nature of the active material SiC NCs. The working electrode also consists of four characteristic peaks at 38.05°, 44.29°, 64.44° and 77.35° correspond to (111), (200), (220) and (311) planes of cubic phase of Ag (JCPDS ICDD no. 11164) along with three peaks at 31.97°, 33.81°, and 58.92° correspond to hexagonal phase of Al2O3 (JCPDS ICDD no. 20921). In addition, the Raman spectrum of the active material shows the five characteristics peaks of SiC nano-cauliflowers at 466, 637, 990, 1375, and 1547 cm−1 (Figure 3b). The broad peak at 466 cm-1, corresponds to a-Si clusters (Si–Si) and the weak band at 637 cm-1 is assigned to Si–Si vibration modes28. The weak band at 990 cm-1 corresponds to longitudinal optical (LO) vibration of Si-C bond29-30. The band centered at 1375 cm-1 is due to disorder in the graphitic clusters sp2 C–C bonds of amorphous carbon, and band at 1547 cm-1 is assigned to graphitic bonds (C:C) vibration modes17. Crosssectional and top surface SEM images of SiC working electrode are shown in Figure 4a-b, respectively. The thickness of SiC layer on current collector is around 1000 (±3) nm. The images show the SiC nanostructures in shapes of nano-cauliflower deposited on Ag/AAO substrate. The proposed growth mechanism for nano-cauliflower structure is as follows: Initially, SiC nuclei is produced and adsorbed on the tip of porous AAO substrate. With the increase in deposition time, the growth of SiC nuclei started with the island formation due to slow diffusion and high interaction of SiC adatoms by maintaining the low surface energy31. Eventually, the growth followed radial as well as longitudinal directions by developing the grain boundaries. Here, the bottom of AAO is less covered, due to the shadow effect of the porous AAO. Finally, the nanostructures develop a cauliflower like structure covering entirely the AAO tips. Figure 4c shows the elemental mapping on the working electrode. All elements are uniformly distributed


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on the electrode surface. The EDX measurements show that active material layer contains about 50.39 atomic% Si, and 49.61 atomic% C (Figure S1a-b). 3.2 Electrochemical properties of working electrode The CV measurements were performed to examine the working electrode using a three-electrode cell in 1 M Na2SO4 aqueous solution at the scan rate of 5-100 mV/s with a potential range from 0.1 to +0.9 V versus Ag/AgCl reference electrode (Figure 5a). The CV plots have an almost ideally rectangular shape, without clear redox peaks, which indicates an ideal capacitive behavior of SiC NCs10, 32-33. As shown in Figure S2a, the working electrode swept larger integral area at high scan rate as compared with current collector, indicating that SiC NCs are the major contributor for the electrochemical performance. The specific capacitance Cs values at different scan rates (5, 20, 50, and 100 mV/s), were found to be 300, 232, 157 and 150 F/g, respectively (Figure S2b). Generally, the energy storage mechanism of the SiC based EDLCs is attributed to the formation of an electric double layer between SiC active material and Na2SO4 electrolyte, which works as the dielectric. By applying voltage to the facing electrodes, ions from the electrolyte (ܰܽ ା , ܱܵସଶି ) are drawn to the electric double layer and EDLC is charged. On the contrary, the ions move away from the electric double layer during discharging the supercapacitor17. Therefore, the capacitance of EDLC is proportional to the surface area of electric double layer i.e. larger the exposed area, higher the capacitance21. Figure 5b shows the GCD curves of working electrode at different current density within a voltage window of 1V. The GCD curves display the almost symmetric charge and discharge curves, revealing excellent electrochemical reversibility and electric double-layer capacitive contribution due to the connective porous structure22. The Cs values at different current density 7 ACS Paragon Plus Environment


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(1.43, 3.57, 7.14, and 10.71 A/g), were found to be 283, 264, 157 and 139 F/g, respectively (Figure S2c). The specific capacitance values in present case indicate the enhanced capacitive performance compared with the previously reported works in the literature (Supplementary Information Table S1). Such high specific capacitance is attributed to the unique 3-D nanostructure of SiC NCs, which significantly decreases the internal resistance of working electrode by the formation of a conductive network and favours the accumulation of the electric double layers6, 34-36. According to the EIS plots in Figure 5c, the charge transfer resistance (Rct) and equivalent series resistance (Rs) of working electrode were only 1.77 and 1.91 Ω, which suggested excellent ion conductivity for the device fabrication37-38. 3.3 Electrochemical properties of symmetric device Figure 6a shows a schematic representation of symmetric supercapacitor device, assembled by two working electrodes. The CV plots in Figure 6b, show the variation of electrochemical investigation of the fabricated supercapacitor device at different scan rates (5-100 mV/s) in 1M Na2SO4 solution. The CV plots show the EDLC behavior of symmetric device with nearly a rectangular shape even at a potential window up to 1.8V (Figure S3a). The device delivers the high specific capacitance values of 188, 73, 57, and 48 F/g; and at scan rate of 5, 20, 50, and 100 mV/s, respectively (Fig. S3b). As shown in Figure 6c, the GCD curves of the supercapacitor device at different current densities are plotted, as a voltage-time profile. The Cs values at different current density (1.43, 3.57, 7.14, and 10.71 A/g), were found to be 72, 64, 56, and 41 F/g, respectively (Figure S3c). The cycling stability of the supercapacitor was tested through a GCD process at current density of 10.71 A/g, as shown in Figure S3d. The device demonstrated an excellent stability, retaining its 97.05% of initial capacitance after 30,000 cycles. No significant electrochemical changes were observed after the prolonged process, justifying the 8 ACS Paragon Plus Environment

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importance of porous, SiC NCs for supercapacitor device integration21. For the symmetric device, the energy and power densities were calculated from GCD curves and plotted on the Ragone diagram as shown in Figure 6d. Several energy densities can be reached with corresponding power densities: 31.43 Wh/kg at 2.5 kW/kg, 27.9 Wh/kg at 6.28 kW/kg, 24.38 Wh/kg at 12.19 kW/kg, and 17.76 Wh/kg at 18.8 kW/kg. The maximum energy density of 31.43 Wh/kg is achieved at a power density of 2.5 kW/kg, while the highest power density is 18.8 kW/kg at the energy density of 17.76 Wh/kg39. As shown in Figure 6e, Nyquist plot of the symmetric device was analyzed by EIS, in the frequency range from 10 mHz to 10 kHz. The magnitude of series resistance Rs and charge-transfer resistance Rct were found to be 2.47 and 2.65 Ω respectively, showing a low internal resistance for the symmetric device but higher than that of the three electrode configuration due to the additional contact resistance of the separator between the two electrodes19. It corroborate that SiC NCs morphology has much better electrochemical performance for the application of supercapacitor35, 40. 4. Conclusion In summary, symmetric supercapacitor based on SiC nano-cauliflowers structure was fabricated by reactive DC sputtering technique. Sputtering was also shown as a versatile and facile method to achieve such high performance contamination and binder free electrodes on a large scale. The energy density of 31.43 Wh/kg and power density of 18.8 kW/kg with excellent capacitive retention (97.05% after 30,000 cycles) demonstrated that the device has excellent stability in a broad potential window of 1.8 V for its practical use in energy storage management for large scale and lightweight electronics. ASSOCIATED CONTENT 9 ACS Paragon Plus Environment


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Supporting Information Figure S1: EDX spectra of working electrode. Figure S2: CV curve of current collector and working electrode, specific capacitance of SiC working electrode calculated from CV and GCD curves. Figure S3: CV curve of symmetric device, specific capacitance of symmetric device calculated from CV and GCD curves, and capacitance retention performance of symmetric device. Table S1: Comparison of the specific capacitance of various SiC nanostructures based supercapacitor electrodes reported in the literature. Calculation of active material mass on working electrode, capacitance, energy density and power density for symmetric supercapacitor cell. ACKNOWLEDGEMENT The author Amit Sanger would like to acknowledge the financial support from the Ministry of Human Resource, India (Grant Code: MHR02-23-200-429). AUTHOR INFORMATION Corresponding Authors *Email: [email protected], [email protected] Conflict of Interests The authors declare no competing financial interests. References (1). Ji, H.; Zhao, X.; Qiao, Z.; Jung, J.; Zhu, Y.; Lu, Y.; Zhang, L. L.; MacDonald, A. H.; Ruoff, R. S., Capacitance of carbon-based electrical double-layer capacitors. Nat. Commun. 2014, 5. 10 ACS Paragon Plus Environment

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FIGURES FIGURE 1

Figure 1. Schematic illustration of the fabrication process of porous alumina by electrochemical anodization.


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FIGURE 2

Figure 2. Schematic illustration of the fabrication process of silicon carbide nano-cauliflowers on porous alumina by DC magnetron cosputtering.



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FIGURE 3

Figure 3. (a) XRD pattern, and (b) Raman Spectra of SiC nano-cauliflowers working electrode.


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FIGURE 4

Figure 4. (a) Cross-section image, (b) top surface image, and (c) EDX elemental mapping of SiC nano-cauliflowers working electrode.



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FIGURE 5

Figure 5. (a) CV curve of Ag/AAO current collector and SiC nano-cauliflowers working electrode at scan rate of 100 mV/s, (b) CV curves of SiC nano-cauliflowers working electrode at different scan rates ranging from 5 to 100 mV/s, (c) GCD curves of SiC nano-cauliflowers working electrode at different current densities, and (c) Nyquist plot with an area of 1 cm2.


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FIGURE 6



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Figure 6. (a) Schematic presentation of the fabricated symmetric supercapacitor device based on SiC nano-cauliflowers working electrode, (b) CV curves for the assembled symmetric device measured with different scan rates, (c) GCD curves of supercapacitors device at different current densities, (d) Ragone plot of the supercapacitor device, and (e) Nyquist plot of the symmetric supercapacitor device.


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