Faculty Publications
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Item Comparative Studies on Crystalline and Amorphous Vinylidene Fluoride Based Fibrous Polymer Electrolytes for Sodium-Ion Batteries(Springer Singapore, 2020) Janakiraman, S.; Khalifa, M.; Biswal, R.; Ghosh, S.; Anandhan, S.; Adyam, A.In the present work, electrospun poly (vinylidene fluoride) (PVDF) and poly (vinylidene fluoride-co hexafluropropylene) (P(VdF-co-HFP)) fibrous membranes have been compared. Porous homo and copolymer fiber-based membranes with an interconnected structure, high porosity, large electrolyte uptake were prepared by an electrospinning route. The effect of crystallinity in terms of X-ray diffraction (XRD) was investigated for the fibrous polymer membranes (FPMs). The surface morphology of the FPMs is evaluated by field emission scanning electronmicroscopy (FESEM). The FPMswere soaked in 1MNaClO4-ethylene carbonate (EC)/diethyl carbonate (DEC) (1:1, vol%) solution to form fibrous polymer electrolytes (FPEs). The ionic conductivity of copolymer showed 1.126 mS cm−1 under ambient temperature (at 28 °C) higher than the homopolymer (0.79 mS cm−1) because of HFP unit. The electrochemical stability window of the copolymer membrane also enhanced and stable up to 4.9 V versus Na+/Na suitable for high voltage sodium rechargeable batteries. When tested with Na066Fe0.5Mn05O2 as cathode and Na metal as an anode, the cycle performance significantly improved for the copolymer. © Springer Nature Singapore Pte Ltd. 2021.Item Assessment of Ionic Composition of Fresh Cement Blends System with Addition of SCMs and Conductive Materials(Springer Science and Business Media Deutschland GmbH, 2024) Rakesh Kumar, N.; Sundaramoorthi, S.; Palanisamy, T.In this experimental study, an attempt has been made to investigate the effect on the ionic composition of cement system at early age upon the addition of supplementary cementitious materials (SCMs) and conductive additives. The ionic composition of cement system refers to the type and concentration of ionic species and it varies depending on the type of cement and degree of hydration. Cement system containing fly ash, silica fume, and ground granulated blast furnace slag (GGBS) in different proportions were blended to examine the effect of SCMs on the ionic concentration. Apart from SCMs, conductive additives like graphite powder and inorganic salt were also included in the study. The pore solution, formed as a result of the hydration of cement, contains a complex mixture of ions. The ionic conductivity of the pore solution is determined from the concentration of various ionic species. Ionic conductivity is responsible for the electrical, chemical, and mechanical performance of the cement system, and hence, understanding the same is essential. Pore solution is extracted in the early age of the hydrating cement system by centrifugation, and with ion chromatographic technique, the concentrations of ions in the pore solution are determined and the results and discussion are compiled in this paper. From the study, silica fume and magnesium-based salt were observed to be an effective additive in improving the conductivity of the pore solution. © The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2024.Item Sodium ion incorporated alumina - A versatile anisotropic ceramic(Elsevier Ltd, 2019) Pujar, P.; Gupta, B.; Sengupta, P.; Gupta, D.; Mandal, S.The present article is a review of crystal structure dependent anisotropic properties of β and β″-phases of sodium ion incorporated alumina. The anisotropy in electrical properties such as ionic conductivity and dielectric permittivity is due to the layered structure. Conducting plane between two consecutive spinel aluminas constituting loosely bound mobile sodium ions, promote ionic conductivity in the parallel direction. In contrary, the restricted movement of ions in the orthogonal direction brings about polarization giving it directional dielectric property. High ionic conductivity of 1.3 S/cm and large dielectric constant of ˜ 200 are reported. Exchanging sodium ions with different cations, such as potassium and lithium, results in similar anisotropy. The processing of β and β″-phases along with metastability of intermediate mullite phase is described in the current review. In addition, the applications of sodium ion incorporated aluminas, such as solid electrolyte in batteries, thin film transistors and gas sensors are discussed. © 2019 Elsevier LtdItem Potential of pyrochlore structure materials in solid oxide fuel cell applications(Elsevier Ltd, 2021) Anjana, A.P.; Prasad Dasari, H.P.Pyrochlore structure material (A2B2O7) has gained interest in diverse applications like catalysis, nuclear waste encapsulation, sensors, and various electronic devices due to the unique crystal structure, electrical property, and thermal stability. This review deals with the ionic/electronic conductivity of numerous pyrochlore structure materials (titanates, zirconates, hafnates, stannates, niobates, ruthenates, and tantalite based pyrochlore) as electrolyte and electrode materials for solid oxide fuel cells (SOFCs). The impact of cation radius ratio (rA/rB) on the lattice constant and oxygen ‘x’ parameter of different pyrochlore structure materials obtained by various synthesis methods are reported. Higher ionic conductivity is essential for better ion transport in an electrolyte, and mixed ionic and electronic conductivity in electrode is essential for attaining higher efficiency in a typical SOFC. GdxTi2O7-δ, Gd2-xCaxTi2O7-δ, Nd2-yGdyZr2O7, Y2Zr2O7, Y2Zr2-xMnxO7-δ, SmDy1-xMgxZr2O7-x/2, Gd2-xCaxTi2O7-δ pyrochlore are reported as electrolytes for fuel cell applications. Some pyrochlore material (La2-xCaxZr2O7, Sm2-xMxTi2O7 (M = Mg, Co, and Ni) pyrochlore) shows protonic conductivity at lower temperatures and ionic conductivity at higher temperature condition. Also, the mixed ionic-electronic conductivity behavior is reported in electrode materials for SOFC such as R2MnTiO7 (R = Er and Y), R2MnRuO7 (R = Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y), R2Ru2O7 (R = Bi, Pb and Y), Y2-xPrxRu2O7, Ni-(Gd0.9Ca0.1)2Ti2O7-δ, (Gd0.9Ca0.1)2Ti2O7-δ, Gd2(Ti0.8Ru0.2)2O7-δ, (Sm0.9Ca0.1)2Ti2O7-δ and (Y0.9Ca0.1)2Ti2O7-δ pyrochlore. The detailed study of the electronic behavior of these pyrochlore system confirms the necessity of defect structure with high oxygen mobility, lower activation energy, ionic radii ratio criterion should satisfy, and possess notable ion-ion interaction. Ionic conductivity in pyrochlore is increased by enhancing the oxygen migration through 48f-48f site with the formation of oxygen vacancy. Vacancy formation can be achieved by adding a suitable dopant that creates oxygen vacancy by charge compensation mechanism or as anion Frenkel defects. Similarly, the electrical conductivity is improved while adding suitable dopant (Ce, Pr, Ru, etc.) due to disordered structure and anti-Frenkel defect formation which leads to oxygen vacancy formation and thus improves conductivity. © 2020 Elsevier Ltd and Techna Group S.r.l.Item 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.Item 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).Item 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.Item Synthesis of GDC electrolyte material for IT-SOFCs using glucose & fructose and its characterization(Elsevier B.V., 2017) Medisetti, S.; Ahn, J.; Patil, S.; Goel, A.; Bangaru, Y.; Sabhahit, G.V.; Babu, G.U.B.; Lee, J.-H.; Prasad Dasari, H.P.Nano-powder of gadolinium-doped-ceria (GDC, Ce0.9Gd0.1O2) has been synthesized using a novel sol–gel method with glucose and fructose as organic additives. The main objective of the present study is to find the suitability of this synthesis method in synthesizing ceria-based SOFC electrolyte materials and evaluate its performance. The average crystallite/particle size obtained from XRD, TEM, BET surface area was found to be 4–12 nm. The phase was found to be cubic fluorite from XRD and further the structure and the nature of oxygen vacancies was confirmed using Raman spectroscopy. Dilatometer studies illustrated two shrinkage maxima (450 °C and 1450 °C). The ionic conductivity measurements were done using DC four-probe method on the GDC electrolyte sintered at 1500 °C. The sintered sample showed an ionic conductivity of 1.13E?02 Scm?1 at a temperature of 700 °C in the air, and the activation energy is 1.02 eV. The present study reveals that this synthesis method can be adaptable for synthesizing SOFC electrolyte materials. © 2017 Elsevier B.V.Item 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.Item A new strategy of PVDF based Li-salt polymer electrolyte through electrospinning for lithium battery application(Institute of Physics Publishing helen.craven@iop.org, 2019) Janakiraman, S.; Surendran, A.; Ghosh, S.; Anandhan, S.; Adyam, A.Polyvinylidene fluoride (PVDF) ultrafine fibers with different proportions of lithium nitrate (LiNO3) were fabricated by an electrospinning device. The processing parameters are optimized to 19 wt% PVDF to get a bead free structure. Scanning electron microscope (SEM) and atomic force microscope (AFM) showed the uniform and interconnected porous structure. With the addition of 2 wt% LiNO3, the fiber diameter of the electrospun membrane decreased from 371 to 222 nm. Furthermore, the addition of LiNO3 into the nanofibrous membrane enhanced the ionic conductivity from 0.97 ×10-3 S cm-1 to 1.61 ×10-3 S cm-1 at room temperature after soaking with 1 M LiPF6 (lithium hexafluoro-phosphate) in ethylene carbonate (EC) and diethyl carbonate (DEC) in (1:1 wt%). Compared with the conventional Celgard and pristine PVDF membrane, the salt doped PVDF membranes showed higher electrochemical stability window and lower interfacial resistance. The electrospun membrane separators (ES) were assembled into Lithium cobalt oxide (LiCoO2) as cathode and lithium metal as an anode. The salt doped membrane showed superior discharge, C-rate and stable cycle performance than the commercial Celgard membrane. © 2018 IOP Publishing Ltd.