Faculty Publications
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Item Organic-inorganic hybrid mixed-valent bisphosphonate-polyoxovanadates composites with activated carbon for energy storage applications(Nova Science Publishers, Inc., 2024) Madhusree, J.E.; Banerjee, A.; Mal, S.S.In this book, we discuss the investigation of two different bisphosphonate-functionalized polyoxovanadate compounds for use in electrochemical energy storage applications. The compounds are (NH4)4[H6(VIVO2)(VV2O5)2O3P-C(O)(CH2-2-C5NH4)-PO32].9H2O (m), and (NH4)4[H6(VIVO2)(VV2O5)2O3P-C(O)(CH2-3-C5NH4)-PO32]. 8H2O (n). They have a mixed-valent oxovanadate polyanionic assembly that has two different pyridyl functional groups present on the organic bisphosphonate ligand. Several techniques have been used to characterize composites made from these compounds with activated carbon, including Fourier transform infrared spectroscopy, P-XRD, FESEM, EDX, and surface adsorption-desorption tests. The electrochemical performance of acidic electrolytic solutions containing 0.1 M H2SO4, AC-m, and AC-n electrode materials was investigated. Although the compounds are isotypic mixed-valence polyoxovanadate structures, their electrical behavior varies based on the position of the pyridyl group. AC-n was reported to have the most prominent specific capacitance of 313 F g-1 at a current density of 1 A g-1 in a voltage window of 0-1 V, with exceptional energy and power densities of 43.56 Wh kg-1 and 1999.72 W kg-1, respectively. At the same time, AC-m exhibited a specific capacitance of 212 F g-1 and a specific energy of 29.45 Wh kg-1. By lighting up different LED lights with only 42 mg of carbon clothcoated sample, the composite AC-n electrode displayed exceptional specific power. A further benefit of AC-n nanohybrids is their ability to retain electrochemical performance over time, which suggests long-term stability. © 2024 Nova Science Publishers, Inc. All rights reserved.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 Enhanced Power Density of Graphene Oxide–Phosphotetradecavanadate Nanohybrid for Supercapacitor Electrode(Springer, 2021) Maity, S.; Anandan Vannathan, A.A.; Kumar, K.; Das, P.P.; Mal, S.S.Successful exploration of supercapacitor (SC) material to integrate with high energy and high power density storage device still remains a daunting challenge. Conducting carbon nanostructures have been primarily used for this purpose; however, most of their surface area remains unutilized throughout the storage process. Herein, a new type of hybrid material has been reported by effectively using active sides of carbon nanostructures. Insertion of faradaic-type polyoxometalates (POMs), namely phosphotetradecavanadate (Na7[H2PV14O42], hereafter described as PV14), into the graphene oxide (GO) matrix creates a novel hybrid material for SC applications. Owing to the formation of nanohybrid, it can store charges both electrostatically and electrochemically. PV14/GO composite’s electrochemical behavior in different electrolyte (acidic/neutral) solutions shows different types of characteristics. The PV14/GO composite as a working electrode exhibits a high galvanostatic capacitance of 139 F/g while maintaining at a power density of 97.94 W/kg in 0.25 M H2SO4 electrolyte. The specific energy density was also found out to be around 56.58 Wh/kg at a 5 mV/s scan rate for the same electrolyte. Furthermore, in 1 M Na2SO4 solution, PV14/GO composite demonstrates a specific capacitance of 85.4 F/g at a scan rate of 5 mV/s. The equivalent series resistance for the device was found to be approximately 0.51 ? with a circuit resistance of 3.881 ?, using electrochemical impedance spectroscopy. The cell capacitance, employing the Nyquist plot, was calculated to be around 2.78 mF. © 2021, ASM International.Item 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 Imidazolium cation linkers of polyoxomolybdate-polypyrrole nanocomposite electrode-based energy storage supercapacitors(Elsevier Ltd, 2022) Muhammed Anees, P.K.; Anandan Vannathan, A.A.; Abhijith, M.B.; Kella, T.; Shee, D.; Mal, S.S.The electrochemical properties of a new hybrid electrode, liquid-polyoxometalate-polypyrrole (BMIM-PVMo11-PPy) have been studied. The H4[PVMo11O40] (PVMo11) was combined with 1-Butyl-3-methyl-imidazolium (BMIM) ionic liquid and then doped on the polypyrrole (PPy) surface. In order to investigate the interaction between the BMIM, PVMo11, and PPy compound was characterized using various analytical techniques, such as Infrared spectroscopy, thermal stability analysis, powder X-ray diffraction, multinuclear NMR (1H and 13C), FESEM, EDX, and surface adsorption studies. The electrochemical performance of the BMIM-PVMo11-PPy composite material has been tested in an aqueous 0.25 M H2SO4 electrolytic solution. The BMIM-PVMo11-PPy composite exhibits the highest specific capacitance of 527.39 F g−1 at a current density of 1 A g−1, along with remarkable specific energy and power of 51.07 Wh kg−1 and 1078.96 W kg−1, respectively. The BMIM-PVMo11-PPy composite was observed to light up red and blue color LED bulbs for 66 and 16 s, respectively, with 84 mg of sample coated on carbon cloth, suggesting an incredible specific power of that material. © 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 Supercapacitor activity studies of a unique triangular oxo-vanadate-bisphosphonate composite with activated carbon(Springer Science and Business Media Deutschland GmbH, 2022) Thakre, D.; Anandan Vannathan, A.; Banerjee, A.; Mal, S.S.Electrochemical studies have been performed on a hybrid inorganic–organic oxo-vanadate (IV)-bisphosphonate assembly, viz. (NH4)2[H6(VIVO)3(O){O3P-C(OH)(CH2-4-C5NH4)-PO3}3]•26H2O [V3-BP]. The compound has a triangular shaped structure consisting of reduced vanadium (IV) with 1-hydroxo-2-(4-pyridyl) ethylidene-1,1-bisphosphonic acid. Composites of this compound were prepared with activated carbon (AC), viz. AC-V3-BP, and extensively characterized using various analytical techniques (e.g., FT-IR, TGA, P-XRD, FESEM, EDX, and BET) to study the interaction of V3-BP with the activated carbon support. Electrochemical properties of AC-V3-BP were studied, vis-à-vis its supercapacitor behavior, with the electrochemical performance of the composite AC-V3-BP material tested in 0.1 (M) H2SO4 aqueous electrolytic solution. The composite exhibits a specific capacitance of 140.8 F g−1 with a specific energy of 19.56 W kg−1. With such interesting capacitive properties, electrochemical cells prepared with this material were observed to light up red and blue LED bulbs for 90 and 20 s, respectively, suggesting a substantial power density of the materials. The respective electrode prepared from the composite was also observed to retain 79.23% of the electrode stability after 4500 cycles. © 2022, The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.Item Phosphomolybdic acid embedded into biomass-derived biochar carbon electrode for supercapacitor applications(Elsevier B.V., 2023) J.e, M.; Chandewar, P.R.; Shee, D.; Mal, S.S.In high-performance, clean, safe, and cost-effective ways, supercapacitors are among the most promising ways to store and release nonfossil energy. In recent years, renewable biomass-derived activated carbon has been explored as a potential option for electrode material. It restricts their specific capacitance despite being environment-friendly and possessing intrinsic mechanical strength. In order to overcome this limitation and preserve all other properties, we are infusing polyoxometalate into the activated carbon; this increases specific capacitance with its fast reversible redox behaviour and preserves the carbon's characteristics. Beside suffusing phosphomolybdic acid (PMA) into biomass waste material, such as orange peel-derived activated carbon (OPAC), a new hybrid material (OPAC-PMA) was developed. The nanohybrid design was revealed by structural and morphological research, which showed high interfacial contact, allowing polyanions to redox rapidly. The novel hybrid electrode material (OPAC-PMA) has a capacitance value of 66% higher than the bare OPAC electrode. A further study showed that OPAC-PMA composite showed 88.23% cycle stability in 0.5 M H2SO4 electrolyte at 6 A g−1 for 4000 cycles. © 2023 Elsevier B.V.