Faculty Publications
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Item Improved electrochemical performance of graphene oxide supported vanadomanganate (IV) nanohybrid electrode material for supercapacitors(Elsevier Ltd, 2020) Kumari, S.; Maity, S.; Anandan Vannathan, A.A.; Shee, D.; Das, P.P.; Mal, S.S.Graphene oxide (GO)-supported polyoxometalates (POMs) have been considered as promising electrode materials for energy storage applications due to their ability to undergo fast and reversible redox reactions. Herein, vanadomanganate-GO composites (K7MnIVV13O38.18H2O-GO with 2:1 and 4:1 ratio) were investigated for use as potential electrode materials in supercapacitors (SCs). The K7MnIVV13O38.18H2O (MnV13) was synthesized and anchored on GO through electron transfer interaction and electrostatic interaction to make the composite electrodes for the present study. All synthesized electrode materials were fully characterized by various techniques, e.g., Fourier Transform Infrared (FTIR) Spectroscopy, Powder X-ray Diffraction (XRD), Scanning Electron Microscopy/Energy Dispersive X-ray Spectroscopy (SEM/EDS) and High Resolution-Transmission Electron Microscopy (HR-TEM). The electrochemical properties of MnV13/GO composites with different MnV13/GO ratios were investigated by two-electrode cyclic voltammetry (CV) and galvanostatic charge/discharge (GCD) in different electrolytes. The MnV13/GO composite of ratio 2:1 in 1 M LiCl electrolyte and that of ratio 4:1 in 1 M Na2SO4 electrolyte showed significant specific capacitance values of 269.15 F/g and 387.02 F/g, respectively and energy density of 37.38 Wh/kg and 53.75 Wh/kg, respectively for a scan rate of 5 mV/s. Interestingly, the 1:1 (MnV13/GO) composite in 1 M Na2SO4 and 1 M LiCl electrolytes showed very low specific capacitance values as the deposition of MnV13 on GO was not sufficient, as indicated by FTIR and SEM. Thus, it is evident that the specific capacitance value of these composite materials depends on the amount of MnV13 deposited on GO and these composite materials exhibit the potential to improve the performance of GO-based SCs. © 2019Item In situ vanadophosphomolybdate impregnated into conducting polypyrrole for supercapacitor(Elsevier Ltd, 2020) Anandan Vannathan, A.A.; Maity, S.; Kella, T.; Shee, D.; Das, P.P.; Mal, S.S.The fast modernization and advancement in lifestyle increase the consumption of power daily due to all innovative technologies, e.g., hybrid vehicles, solar cells, smart power grid, communication devices, artificial hearts, etc. Conducting organic polymer-based energy storage devices had attracted much attention due to the conductive nature for a long time. However, its application has been restricted because of swelling and shrinking capability during the charge and discharge cycle. The combination of redox-active inorganic metal oxides, such as polyoxometalates (multi-metal oxide cluster) with conduction polymers, could enhance the material's stability due to its fast multi-electron redox property. Here, we report the two polypyrroles combined vanadophosphomolybdates, namely PPy-H4[PVMo11O40] and PPy-H5[PV2Mo10O40] nanohybrid electrode materials. The PPy-H5[PV2Mo10O40] electrode material behaves as pseudocapacitance and can deliver an excellent capacitance of 561.1 F/g in 0.1 M H2SO4 electrolyte solution at a 0.2 A/g current density, indicating capacitive composite material. The electrochemical impedance spectroscopy (EIS) reveals that PPy-H5[PV2Mo10O40] is more capacitive than PPy-H4[PVMo11O40] and PPy with equivalent series resistance (ESR) of 5.74 ?. The cell capacitance of PPy-H5[PV2Mo10O40] and PPy-H4[PVMo11O40] are found to be 5.38 and 9.15 mF, stipulating in small SC cell application. Likewise, the PPy-H5[PV2Mo10O40] nanohybrid electrode shows better responsive behavior with a relaxation time of 0.16 ms. Furthermore, the PPy-H5[PV2Mo10O40] electrode exhibits outstanding cycle stability, retaining ~95% of its capacitance after 4500 cycles as compare to PPy-H4[PVMo11O40] (~91%) electrode. © 2020Item Activated carbon- supported Vanado-nickelate (IV) based hybrid materials for energy application(Elsevier Ltd, 2021) Maity, S.; BM, N.; Kella, T.; Shee, D.; Das, P.P.; Mal, S.S.The rapid development of supercapacitor (SC) technology leads to increased demand for nanofabrication of novel and effective electroactive hybrid materials for next-generation energy storage devices. Herein, nickel tetradecavanadate, K2H5[NiV14O40](NiV14), is doped into porous activated carbon (AC), for the first time, in different wt.% in order to investigate the homogeneous loading of the inorganic metal-oxide component on the AC matrix. The resulting complex, AC-NiV14, is found to have possessed an enhanced electrochemical characteristic (for both symmetric and asymmetric SC cell), which operates at a significantly higher potential of 1.2 V. The combination of the double-layer capacitance (EDLC) and the redox-active polyoxometalate cluster leads to an intrinsic increase in specific capacitance (capacity) (from 45.3 Fg?1 (54.4 Cg?1) for AC to 316 Fg?1 (379.2 Cg?1) for 15 wt.% AC-NiV14 at a current density of 1 Ag?1). It was also observed that there is an increase of 20% in the operating voltage compared to conventional AC supercapacitors with acidic aqueous electrolytes. Firstly, symmetric supercapacitor's electrochemical performances of various wt.% of NiV14 composition were studied in acidic aqueous electrolyte (0.5 M H2SO4) solution. We observed that the 15 wt.% of AC-NiV14 hybrid electrode showed remarkable specific energy value (~63.2 Wh kg?1) compared with pristine AC and NiV14 electrodes, separately. Besides, the asymmetric layout (AC//AC-NiV14) increased the potential window up to 1.5 V and enhanced the specific energy and power values (90.1 Whkg?1 and 2400 Wkg?1, respectively), with 98% coulombic efficiency. Meanwhile, the AC-NiV14//NiV14 asymmetric cell possesses a specific capacitance (capacity) of 375 Fg?1 (450 Cg?1) with a maximum power of 3140 Wkg?1 at the high current density of 2 Ag?1. © 2021 Elsevier LtdItem Organic cation linkers polyoxomolybdate-polypyrrole nanocomposite-based supercapacitors(Springer Science and Business Media Deutschland GmbH, 2021) Muhammed Anees, P.K.; Anandan Vannathan, A.; Kella, T.; Shee, D.; Mal, S.A few new hybrid electrode materials have been synthesized and immobilized for the next-generation energy storage device. The hybrid electrodes PVMo11-TBA, PVMo11-BTA, PVMo11-TBP, PVMo11-TBA-PPy, PVMo11-BTA-PPy, and PVMo11-TBP-PPy were well characterized by NMR, XRD, FTIR, FESEM, BET, and tested for electrochemical performance. Among these hybrid electrode materials, the PVMo11-TBA-PPy electrode shows a high specific capacitance of 144.37 F/g at a 1A/g current density and incredible power and energy density of 1100.16 W/kg and 15.28 Wh/kg, respectively. The high electrode’s capacitance was due to the synergistic effect between the PPy and TBA-PVMo11 and high ionic diffusion compared with other synthesized electrodes. It also exhibited high cycle stability of 72.78% after 4500 cycles at 1 M H2SO4 electrolyte. The EIS offers a lower ESR value of 0.72 ohms for the PVMo11-TBA-PPy than PVMo11-TBA, indicating the rapid charge/discharge rate. On the other hand, the PVMo11-BTA-PPy and PVMo11-TBP-PPy electrodes showed lower capacitance values of 26.98 and 19.53. F/g at 0.4 and 1 A/g current density, respectively. Lowering the capacitance could be the prevention of the interaction of organic cations with the counter polyanion. © 2021, The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.Item Electrochemical performance of activated carbon-supported vanadomolybdates electrodes for energy conversion(Elsevier Ltd, 2021) Maity, S.; Anandan Vannathan, A.; Kella, T.; Shee, D.; Das, P.P.; Mal, S.Reinforcing polyoxomolybdates (POMs) into the activated carbon (AC) template engenders a nanohybrid electrode material for high-performance supercapacitor applications. Herein, a first-time novel integration of two polyoxometalates ([PVMo11O40]4-, [PV2Mo10O40]5-) with AC has been demonstrated, and their structural and electrochemical performances were analyzed. AC-VMo11 composite displayed an enhanced capacitance of 450 Fg-1 with an improved energy density of 59.7 Whkg-1. Furthermore, the symmetric supercapacitor cell for AC-VMo11 and AC-V2Mo10 showed high cell capacitances of 38.8 and 20.01 mF, respectively, alongside 99.99% capacitance retention of over 5000 cycles. In addition, the influence of ionic liquid as an electrolyte on AC-V2Mo10 based supercapacitor cell was investigated in tetrabutylammonium bromide (TBAB) electrolyte solution. © 2021 Elsevier Ltd and Techna Group S.r.l.Item Polyoxomolybdate-Polypyrrole-Graphene Oxide Nanohybrid Electrode for High-Power Symmetric Supercapacitors(American Chemical Society, 2021) Maity, S.; Je, M.; Biradar, B.R.; Chandewar, P.R.; Shee, D.; Das, P.P.; Mal, S.Supercapacitors have emerged as one of the most promising candidates for high-performance, safe, clean, and economical routes to store and release of nonfossil energy. Designing hybrid materials by integrating double-layer and pseudocapacitive materials is crucial to achieving high-power and high-energy storage devices simultaneously. Herein, we synthesized a polyoxomolybdate-polypyrrole-graphene oxide nanohybrid via a one-pot reaction. The inclusion of polypyrrole enables a uniform distribution of the polyoxomolybdate clusters; it also confines the restacking of graphene oxide nanosheets. The structural and morphological analysis to unveil the nanohybrid architecture implies excellent interfacial contact, enabling fast redox reaction of polyanions, and a quick transfer of charge to the interfaces. Electrochemical characteristics tested under a two-electrode system exhibit the highest capacitance of 354 F g-1 with significantly high specific energy and power of 49.16 Wh kg-1 and 999.86 W kg-1, respectively. In addition, the cell possesses a high-rate capability and long cycle life by maintaining 96% of its capacitance over 5000 sweeping cycles. The highest specific power of ?10 »000 W kg-1 was computed with Coulombic efficiency of 92.30% at 5 A g-1 current density. Electrochemical impedance spectroscopy additionally reveals enhanced redox charge transfer due to double hybridization. Furthermore, it also demonstrates the impedance and capacitive behavior of supercapacitor cells over a definite frequency regime. ©Item Asymmetric polyoxometalate-polypyrrole composite electrode material for electrochemical energy storage supercapacitors(Elsevier B.V., 2022) Anandan Vannathan, A.; Chandewar, P.R.; Shee, D.; Mal, S.Nowadays, metal-oxides impregnated conducting polymers as electrode materials are attracted much attention due to their higher stability. Here, the metal-oxide cluster, polyoxometalate (K5H2[PV4W8O40]·11H2O, PV4W8), was introduced into the polypyrrole (PPy) matrix to overcome the polymers stability issues, and thus, the resulting novel PV4W8/PPy (symmetric) composite electrode has been reported. XPS confirmed the presence of all atoms on the polymer backbone with respective oxidation states. Nevertheless, doping of PV4W8 on the conductive PPy matrix's surface can affectively improve the ion's transfer. Finally, the asymmetric PV4W8-PPy/PPy composite exhibits a prodigious specific capacitance of 291 F g−1, larger than the PPy (90.01 F g−1) and PV4W8 (39.03 F g−1) at 0.4 A g−1 current density. The PV4W8-PPy/PPy (asymmetric) electrode showed excellent cycle stability. However, a symmetric supercapacitor device based on PV4W8/PPy composite possesses a specific capacitance of 195.27 F g−1 and an energy density of 8.94 Wh kg−1 at the same current density as PV4W8-PPy/PPy (asymmetric) electrode with remarkable cycle stability. © 2021 Elsevier B.V.Item Investigations of redox-active polyoxomolybdate embedded polyaniline-based electrode material for energy application(Springer Science and Business Media Deutschland GmbH, 2022) Anandan Vannathan, A.A.; Kella, T.; Shee, D.; Mal, S.S.Higher capacitance supercapacitors have received considerable attention, including their massive power density, high stability, and long cycle life. On the other hand, polymers have been known for their energy storage device application because of the pseudocapacitance behavior resulting from the extended conjugation over the polymer backbone. Here, we report a simple chemical bath deposition method for the synthesis of two polyoxometalates (H4[PVMo11O40] and H5[PV2Mo10O40]) impregnated polyaniline (PAni) composite (PVMo11@PAni and PV2Mo10@PAni) for electrochemical supercapacitors. Various analytical methods characterized the electrode materials, e.g., Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), powder X-ray diffraction (PXRD) method, and the morphological features of those electrodes were acquired by field emission scanning microscopy (FESEM). The exceptionally high average capacitance of 1371 F g−1 was obtained for the composite PVMo11@PAni electrode at a 3 A g−1 current density and 1 V potential window with an energy density of 137.5 W h kg−1. The PVMo11@PAni composite electrode showed almost 4.3 times the higher energy density than pure PAni and 2.3 times higher than PV2Mo10@PAni. In contrast, PV2Mo10@PAni composite showed 1.9 times more energy density than pure PAni composite electrode. Interestingly, high average capacitance, charge–discharge rates, and high energy density with high-level power delivery make them promising electrode candidates for supercapacitors. © 2021, The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.Item Vanadomanganate as a synergistic component in high-performance symmetric supercapacitor(Elsevier Ltd, 2022) Maity, S.; Anandan Vannathan, A.A.; Chandewar, P.R.; Shee, D.; Das, P.P.; Mal, S.S.Supercapacitor devices fabricated from capacitive and battery-type hybrid electrodes have been projected as a promising energy storage system because of their ability to produce high specific power and energy simultaneously. In this work, we have demonstrated a facile method of impregnation of faradaic type manganese (III) polyoxovanadate, [MnV14O40]−6 on the high surface area substrate of activated carbon (AC) as well as graphene oxide (GO). Materials and electrochemical characterizations data confirm the successful incorporation of capacitive and faradaic type manganese (III) polyoxovanadate into the nanohybrid electrode material. Furthermore, the synergic effect between the carbonaceous nanostructures (AC/GO) and redox-active oxometalate (MnV14) provides a better pathway for ion transport to the interface resulting in enhancement of the conductivity, diffusion ability of the nanohybrid. Moreover, the battery-type MnV14 clusters disperse in the micro/mesopores of AC, whereas the oxygen-containing functional groups in GO act as active sites for anchoring of MnV14 clusters. Thus, the surface modification with MnV14 clusters enhances the specific capacitance of nanohybrid with remarkable electrical and mechanical stability. The AC/MnV14 nanohybrid exhibits an enhanced specific capacitance of 547 F g−1 with specific energy and power of 76 Wh kg−1 and 1600 W kg−1, respectively, at 0.8 A g−1 current density. Additionally, GO/MnV14 shows a specific capacitance of 330 F g−1 with improved specific energy and power of 30 Wh kg−1 and 1276 W kg−1, respectively, at the same current density. Moreover, both the nanohybrids possess excellent cycle stability by retaining 92% (AC/MnV14) and 90.6% (GO/MnV14) of initial capacitance even after 5000 sweeping cycles. © 2021 Elsevier B.V.Item Polyoxovanadate-Activated Carbon-Based Hybrid Materials for High-Performance Electrochemical Capacitors(Institute of Physics, 2022) Anandan Vannathan, A.; Chandewar, P.R.; Shee, D.; Mal, S.S.Two different polyoxovanadates derivatives, K5MnIVV11O32.10 H2O (MnV11) and K7MnIVV13O38.18 H2O (MnV13), have been studied to evaluate their electrochemical performance. These polyoxovanadates were deposited on activated carbon (AC) to prepare AC-MnV11 and AC-MnV13 composites. The electrochemical performance of the AC-MnV11 electrode exhibits the remarkable specific capacitance of 479.73 F g-1 at a current density of 0.6 A g-1, along with incredible specific power and energy of 960 W kg-1. Likewise, the AC-MnV13 exhibits a specific capacitance of 357.33 F g-1 at the current density of 0.6 A g-1 with a specific energy of 71.46 Wh kg-1. Interestingly, the AC-MnV11 could light up the red and yellow color LED bulbs for a duration of 80 and 60 s, respectively, indicating a considerable specific power of the material. The AC-MnV13 electrode shows significantly less lighting up during the 65 and 30 s period with red and yellow LED bulbs. © 2022 The Electrochemical Society ("ECS"). Published on behalf of ECS by IOP Publishing Limited.