Faculty Publications

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    Reduced graphene oxide derived from used cell graphite and its green fabrication as an eco-friendly supercapacitor
    (Royal Society of Chemistry, 2014) Sudhakar, Y.N.; Muthu, M.; Bhat, D.; Senthil Kumar, S.
    Graphite extracted from a used primary cell was converted into reduced graphene oxide (rGO) using calcium carbonate together with rapid and local Joule heating by microwave irradiation. Electrodes were prepared by ultrasonically dispersing rGO in biodegradable poly(vinylpyrrolidone) (PVP) binder and coating this on recyclable poly(ethyleneterephthalate) (PET) sheet using a low cost screen printing technique. The use of the same polymer (PVP) as a binder, in addition to as the solid polymer electrolyte (SPE), enhances the compatibility and ionic conductivity of the hydrophobic rGO electrode in the supercapacitor system. Further, the phosphoric acid (H3PO4)-doped biodegradable SPE was screen printed for the first time on the rGO electrodes. Ionic conductivity and dielectric studies of the SPE were carried out at different temperatures and different dopant acid concentrations. The morphology, composition and structure of the graphene electrode components were characterized using Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) methods. Transmission electron microscopy (TEM) images showed a single layer or a few layers of rGO sheets and selected area electron diffraction showed the presence of slight defects. The fabricated environmentally friendly, industrially favorable and green supercapacitor showed a specific capacitance of 201 F g-1 and cyclic stability with 97% retention of the initial capacitance over 2000 cycles. Furthermore, the performance of this green supercapacitor is comparable to that of those fabricated using rGO synthesized from commercial graphite and in other literature reports. © 2014 The Royal Society of Chemistry.
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    Preparation and characterization of phosphoric acid-doped hydroxyethyl cellulose electrolyte for use in supercapacitor
    (SpringerOpen, 2015) Sudhakar, Y.N.; Muthu, M.; Bhat, D.K.
    A new borax cross-linked biodegradable solid polymer electrolyte based on hydroxyethyl cellulose and phosphoric acid (H3PO4) was prepared. Characterizations of doped and undoped SPE were done using Fourier transform infrared spectroscopic and electrochemical studies. The ionic conductivity of the films increased with increase in acid concentration and the ionic conductivity obtained at 303 K was 4.1 × 10-3 S cm-1. Furthermore, effects of acid concentration on ionic conductivity and activation energy were discussed. Dielectric studies showed long tail-like feature indicating capacitive nature. A supercapacitor was fabricated and its electrochemical characteristics were studied. The supercapacitor showed a fairly good specific capacitance of 83 F g-1 at 2 mV s-1 and galvanostatic charge-discharge studies showed the mirror-like pattern with 98 % columbic efficiency. Cyclic stability was measured up to 2000 cycles. © 2015 The Author(s).
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    Ionic conductivity and dielectric studies of acid doped cellulose acetate propionate solid electrolyte for supercapacitor
    (John Wiley and Sons Inc, 2016) Sudhakar, Y.N.; Bhat, D.; Muthu, M.
    Phosphoric acid doped cellulose acetate propionate (CAP) consisting of poly(ethylene glycol) (PEG) as plasticizer was investigated. Ionic conductivities and dielectric studies were carried at different temperature with varying concentration of H3PO4 using AC impedance method. The highest conductivity was 8.1 × 10-4 S cm-1 at 343 K and a long tail was featured in dielectric studies indicating good capacitance nature of the electrolyte. Interactions between added constituents were observed in FTIR and differential scanning calorimetry studies. Thin and compact fabricated supercapacitor demonstrated specific capacitance of 64 F g-1 using cyclic voltammetry. Furthermore, the supercapacitor properties like AC impedance and charge-discharge were studied. Stability was up to 96% at 1000th cycle. POLYM. ENG. SCI., 56:196-203, 2016. © 2015 Society of Plastics Engineers.
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    Record-low sintering-temperature (600 °c) of solid-oxide fuel cell electrolyte
    (Elsevier Ltd, 2016) Prasad Dasari, H.P.; Ahn, K.; Park, S.-Y.; Hong, J.; Kim, H.; Yoon, K.J.; Son, J.-W.; Kim, B.-K.; Lee, H.-W.; Lee, J.-H.
    One of the major problems arising with Solid-Oxide Fuel Cell (SOFC) electrolyte is conventional sintering which requires a very high temperature (>1300 °C) to fully densify the electrolyte material. In the present study, the sintering temperature of SOFC electrolyte is drastically decreased down to 600 °C. Combinational effects of particle size reduction, liquid-phase sintering mechanism and microwave sintering resulted in achieving full density in such a record-low sintering temperature. Gadolinium doped Ceria (GDC) nano-particles are synthesized by co-precipitation method, Lithium (Li), as an additional dopant, is used as liquid-phase sintering aid. Microwave sintering of this electrolyte material resulted in decreasing the sintering temperature to 600 °C. Micrographs obtained from Scanning/Transmission Electron Microscopy (SEM/TEM) clearly pointed a drastic growth in grain-size of Li-GDC sample (?150 nm) than compared to GDC sample (<30 nm) showing the significance of Li addition. The sintered Li-GDC samples displayed an ionic conductivity of ?1.00 × 10-2 S cm-1 at 600 °C in air and from the conductivity plots the activation energy is found to be 0.53 eV. © 2016 Elsevier B.V. All rights reserved.
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    Praseodymium doped ceria as electrolyte material for IT-SOFC applications
    (Elsevier Ltd, 2018) Shajahan, I.; Ahn, J.; Nair, P.; Medisetti, S.; Patil, S.; Niveditha, V.; Uday Bhaskar Babu, G.; Prasad Dasari, H.P.; Lee, J.-H.
    Praseodymium-doped ceria (PDC, Ce0.9Pr0.1O2) electrolyte material for intermediate temperature solid oxide fuel cells (IT-SOFCs) has been successfully synthesised by EDTA-citrate method. From X-Ray diffraction (XRD), fluorite structure along with a crystallite size of 5.4 nm is obtained for PDC nanopowder calcined at 350 °C/24 h. Raman spectroscopy confirmed the structure, presence of oxygen vacancies with the manifestation of the main peak at 457 cm?1 and with a secondary peak at 550 cm?1. From Transmission Electron Microscopy (TEM) analysis, the average particle size is around 7–10 nm and selected area electron diffraction (SAED) patterns further confirmed the fluorite structure of PDC nanopowder. The PDC nanopowder displayed a BET surface area of 65 m2/g with a primary particle size of ?13 nm (calculated from BET surface area). Dilatometer studies revealed a multi-step shrinkage behaviour with the multiple peaks at 522, 1171 and 1461 °C which may be originated due to the presence of multiple size hard agglomerates. The PDC electrolyte pellet sintered at 1500 °C displayed an ionic conductivity of 1.213E-03 S cm?1 along with an activation energy of 1.28eV. Instead of a single fluorite structure, XRD of sintered PDC pellet showed multiple structures (Fluorite structure (CeO2) and cubic structure (PrO2). © 2018 Elsevier B.V.
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    Electrochemical characterization of a polar ?-phase poly (vinylidene fluoride) gel electrolyte in sodium ion cell
    (Elsevier B.V., 2019) Janakiraman, S.; Surendran, A.; Biswal, R.; Ghosh, S.; Anandhan, S.; Adyam, A.
    A polar ?-phase poly (vinylidene fluoride) (PVDF) membrane is developed through the electrospinning method. PVDF gel electrolyte for sodium ion batteries was obtained by saturating the bare porous membrane in a liquid electrolyte, 1 M NaClO4 in EC: DEC (1:1 vol%). The physical and electrochemical characteristics of the polar ?-phase PVDF membrane are explored by X-ray diffraction (XRD), Field emission scanning electron microscopy (FESEM), Atomic force microscope (AFM), sodium ion conductivity, linear sweep voltammetry (LSV) and sodium ion transference number. The ionic conductivity of a polar ?-phase PVDF gel electrolyte exhibited 9.2 × 10?4 S cm?1, higher than the commercially used Celgard® 2400 membrane 0.36 × 10?4 S cm?1 at ambient temperature. The electrochemical expolarations of the sodium ion half-cell (Na2/3Fe1/2Mn1/2O2) as a cathode and sodium metal as a counter electrode) conducted from PVDF gel electrolyte are analysed by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). CV of the battery showed a pseudo capacitive nature. The equivalent circuit model of the sodium ion cell brought out the effect of dipole moments in the polymer chains on the battery performance. © 2018 Elsevier B.V.
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    Effect of sintering aids on sintering kinetic behavior of praseodymium doped ceria based electrolyte material for solid oxide cells
    (Elsevier Ltd, 2020) Shajahan, I.; Prasad Dasari, H.P.; Saidutta, M.B.
    The present study investigates the effect of sintering additives (Li, Co, Fe, and Mg) on the sintering kinetic behavior of the praseodymium-doped-ceria (PDC) electrolyte of solid oxide electrolyzer cell. 3Li-PDC, 3Co-PDC, 3Fe-PDC, and 3 Mg-PDC pellets were obtained from the synthesis of PDC nano-powder by microwave-assisted co-precipitation method using isopropyl alcohol as a solvent and followed by sintering additive wetness impregnation method. Linear shrinkage and shrinkage rate data suggest a positive sintering effect for 3Li-PDC and 3Co-PDC pellets and a negative sintering effect for 3 Mg-PDC and 3Fe-PDC pellets than compared to PDC pellets alone. The addition of lithium as a sintering additive (3Li-PDC) had reduced the sintering temperature of PDC from 1100 °C to 850 °C. For PDC, 3Li-PDC, 3Co-PDC, 3Fe-PDC and 3 Mg-PDC pellets sintered at 1100 °C, 850 °C, 1000 °C, 1200 °C, 1100 °C for 2 h resulted in a relative density of 93.6 ± 0.25, 95.8 ± 0.45, 95.0 ± 0.20, 92.7 ± 0.10, and 94.5 ± 0.10%, respectively. The XRD patterns of the sintered PDC pellets suggested a secondary phase formation (PrO2) in 3Co-PDC, 3Fe-PDC, and 3 Mg-PDC pellets indicating that the addition of these sintering aids results in poor solubility limit of Pr in CeO2. On the other hand, XRD patterns of PDC and Li-PDC sintered pellets displayed no secondary peak indicating good solid-solution formation. The activation energy of the 3Li-PDC pellet is obtained from CHR and Dorn methods and was found to be 182 kJ/mol and 196 kJ/mol. From the CHR method, for the 3Li-PDC pellet, the initial sintering behavior is by the grain boundary diffusion mechanism (m = ~2). © 2020 Hydrogen Energy Publications LLC
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    Dilatometer studies on LAMOX based electrolyte materials for solid oxide fuel cells
    (Elsevier Ltd, 2021) Das, A.; Lakhanlal, u.; Shajahan, I.; Prasad Dasari, H.P.; Saidutta, M.B.; Harshini, H.
    The present study deals with the citrate complexion synthesis of LAMOX-based Solid Oxide Fuel Cell (SOFC) electrolyte materials (La1.8Dy0.2Mo2-xWxO9 (x = 0, 0.1, 0.2, 0.5, and 1), La1.8Dy0.2Mo2-xGaxO9 (x = 0.1 and 0.2), and La1.8Dy0.2Mo2-xVxO9 (x = 0.025, 0.05, 0.1, and 0.2)) and their characterization to understand the sintering behaviour and phase stability. From the dilatometer studies, the linear shrinkage and shrinkage rate of the LDMW (x = 0, and 0.1) showed better shrinkage than LM and LDM. Gallium addition (LDMG) and Vanadium addition (LDMV) showed a negative impact on shrinkage behaviour. In the temperature range of 500–580 °C, the abrupt change in shrinkage rate showed the transition of phase from ? to ? for the LM. The modification of LM to LDM, LDMW, and LDMV suppressed the formation of the ? phase. During thermal expansion behaviour study in the temperature range of 100–500 °C and 550–800 °C, the LM sintered pellet showed the coefficient of thermal expansion (CTE) values of 13.3 ? 10?6/°C and 21.6 ? 10?6/°C respectively. The LDM and LDMW sintered pellets showed the CTE values in the range of 14–15 ? 10?6/°C and 16–19 ? 10?6/°C, respectively. The relative density of the sintered pellets (1100 °C/5 h in air) (LM, LDM, LDMW, and LDMG (x = 0.1)) is found to be >90%. It provides the suitability of these materials for further investigation as electrolytes of SOFCs/SOECs. © 2020 Elsevier B.V.
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    Numerical investigation on the improved reactant mass transport with depth-dependent flow fields in polymer electrolyte fuel cell under inhomogeneous gas diffusion layer compression
    (Elsevier Ltd, 2021) Padavu, P.; Koorata, P.K.; Bhat, S.D.
    In this work, a numerical model is developed to analyse the effects of depth-dependent reactant flow field geometry under inhomogeneous gas diffusion layer (GDL) compression on the mass transport process and performance of polymer electrolyte fuel cell (PEFC). The types of depth-dependent flow channels considered in this study are: converging channel (depth continuously decreasing) and diverging channel (depth continuously increasing), and the conventional flow field designs. The model is investigated for local and global inhomogeneity due to GDL compression. The localized inhomogeneity is introduced in the flow-field rib as well as channel regions. The results are compared for reactant concentration, water concentration, local current density, and the polarization curve for different flow channel combinations. It is observed that the availability of reactants is higher in case of converging channel design, which leads to an increase in cell performance at higher currents. However, this is subjected to GDL inhomogeneity in compression. We observe in this study that such inhomogeneity, instead of having a significant impact on cell performance, lead to minimal influence in terms of reduction in cell performance. This we observe is due to improved H2 availability at anode and reduced O2 distribution at cathode that ultimately impacts respective hydrogen oxidation reaction (HOR) and reduction in oxygen reduction reaction (ORR). This study aims to investigate the cases for altered variation in cell performance due to change in depth-dependent flow fields. © 2021
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    Electrical conductivity studies on LAMOX based electrolyte materials for solid oxide fuel cells
    (Elsevier Ltd, 2022) Srijith; Lakhanlal, u.; Das, A.; Prasad Dasari, H.P.; Saidutta, M.B.
    In this study, the electrical conductivity of the LAMOX based electrolytes (La1.8Dy0.2Mo2-xWxO9 (x = 0, 0.1, 0.2, 0.5, and 1), and La1.8Dy0.2Mo2-xGaxO9 (x = 0.1)) synthesized by the citrate complexion method has been studied using DC four-probe method. The electrical conductivity of the electrolytes is measured in the temperature range of 800–400 °C in the air (∼100 ml min−1). The effect of W and Ga substitution at the Mo site on the electrical conductivity is evaluated. The long-term electrical conductivity stability test (time on stream) (5 h) is conducted at 650, 580, and 520 °C to study the effect of possible phase transition on electrical conductivity. A high-temperature XRD study is also conducted in the temperature range of 500–650 °C (during heating and cooling) on selected electrolyte materials (La1.8Dy0.2Mo2-xWxO9 (x = 0 and 0.1) and La1.8Dy0.2Mo2-xGaxO9 (x = 0.1)) to study the α↔β phase transition. The electrical conductivity of these electrolytes in the air at 800 °C is in the range of 5.3 × 10−2 – 14 × 10−2 S cm−1. The activation energy (EA) of these electrolytes is in the range of 1.11–1.62 eV. The VTF parameters σo, B, and To are in the range of 67.46–395.88 S cm−1 K0.5, 0.122–0.254 eV, and 247–347 °C, respectively. The La1.8Dy0.2Mo2-xWxO9 (x = 0.1) shows highest electrical conductivity (14 × 10−2 S cm−1, EA = 1.54 eV) among all electrolytes in air at 800 °C and for this material the VTF parameters σo, B, and To are 170.32 S cm−1 K0.5, 0.153 eV, and 302 °C, respectively. © 2022 Elsevier Ltd and Techna Group S.r.l.