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    Electroactive poly(vinylidene fluoride) fluoride separator for sodium ion battery with high coulombic efficiency
    (Elsevier B.V., 2016) Janakiraman, S.; Surendran, A.; Ghosh, S.; Anandhan, S.; Adyam, A.
    Electroactive separators are recent interest in self-charging rechargeable batteries. In this study, electrospun polyvinylidene fluoride (PVDF) is characterized as an electroactive separator for Na-ion batteries. The intrinsic ?-phase with high porosity of the separator is confirmed from X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Field emission scanning electron microscopy (FESEM) and Atomic Force Microscopy (AFM) studies. The electroactive separator is immersed in 1M NaClO4-ethylene carbonate (EC)/diethyl carbonate (DEC) (1:1 by weight) solution. The physicochemical characteristics of electroactive separator electrolyte (EaSE) were investigated using sodium ion conductivity, ion transference number and contact angle measurements. Linear and cyclic voltammetry studies were also carried out for the electrolyte system to evaluate oxidation stability window. The inherent ?-phases of the separator as obtained by electrospinning has an ionic conductivity of ~ 7.38 × 10- 4 S cm- 1 under ambient condition. Sodium ion cell made from EaSE with Na0·66Fe0.5Mn0·5O2 as cathode and Na metal as anode has displayed a stable cycle performance with a coulombic efficiency of 92% after 90 cycles. © 2016 Published by Elsevier B.V.
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    Modelling the land use system process for a pre-industrial landscape in India
    (Springer Science and Business Media Deutschland GmbH, 2017) Ghosh, S.; Shetty, A.
    Land in India is changing in a rapid pace since the green revolution during 1960 and industrial policy reforms during 1990. Certainly land cover land use (LCLU) changes have huge impacts on countries overall ecological balance and climate change. The most intriguing fact is LCLU change is an interconnected phenomenon like a system. The understanding of local level LCLU dynamics are yet to get a momentum in India. The present study is an attempt: (1) to examine the land use change drivers active at the studied landscape of coastal Karnataka in India and (2) to model the LCLU changes in pre-industrialized period using Dyna-CLUE model. Binary logistic regression was used to categorize land change drivers and to estimate the probability of changes. Odd ratio from logistic regression indicates that the biophysical drivers are most prominent in determining location of LCLU. They being slope, relative relief, drainage density and availability of ground water are the most influential drivers for most of the land classes. The Dyna-CLUE model is successful to simulate the LCLU change at aggregate level but the spatial allocation needs improvement. © 2017, Springer International Publishing Switzerland.
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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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    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.
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    Electrospun electroactive polyvinylidene fluoride-based fibrous polymer electrolyte for sodium ion batteries
    (Institute of Physics Publishing helen.craven@iop.org, 2019) Janakiraman, S.; Surendran, A.; Biswal, R.; Ghosh, S.; Anandhan, S.; Adyam, A.
    Electrospinning is an efficient technique to produce ultrafine electroactive mat, diameters ranging from few nanometers to micrometers to use as a separator in sodium ion battery. The polyvinylidene fluoride (PVDF) polymer solution was optimized to 19 wt%, applied voltage 25 kV and flow rate of 0.5 ml h-1 to get a bead free ultrafine electroactive structure. The electroactive ?-phase is confirmed by x-ray diffractometer (XRD). Ionic conductivities, electrolyte uptake, wettability, linear sweep voltammetry (LSV) and thermal stability of the electroactive fibrous polymer electrolyte (EFPE) were studied by soaking the separator with a liquid electrolyte of 1 M sodium hexafluorophosphate (NaPF6) dissolved in ethylene carbonate (EC)/propylene carbonate (PC) (1:1 vol%). The EFPE exhibits high ionic conductivity of 1.08 mS cm-1 and electrochemical stability window of 5.0 V versus Na/Na+ under ambient condition. The half-cell containing Na0.66Fe0.5Mn0.5O2 as cathode and EFPE as the separator cum electrolyte showed a stable cycling performance at a current rate of 0.1C. © 2019 IOP Publishing Ltd.
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    PVDF/halloysite nanocomposite-based non-wovens as gel polymer electrolyte for high safety lithium ion battery
    (John Wiley and Sons Inc. cs-journals@wiley.com, 2019) Khalifa, M.; Janakiraman, S.; Ghosh, S.; Adyam, A.; Anandhan, S.
    Gel polymer electrolyte (GPE) based on electrospun poly(vinylidene fluoride) (PVDF)/halloysite nanotube (HNT) nanocomposite non-wovens was synthesized and its suitability as a separator in lithium-ion battery (LIB) was explored. In this study, HNT played a key role in reducing the average diameter of the electrospun fibers and uplifted the porosity of the non-wovens thereby improving their electrolyte uptake. Due to a reduction in crystallinity and increased % porosity of the PVDF/HNT non-wovens, the ionic conductivity (1.77 mScm?1) and ionic transport across the separator were improved. Moreover, this GPE separator exhibited high tensile and puncture strength with negligible thermal shrinkage and a higher melting temperature compared with a commercially available separator, which is vital from the safety perspective. The cycling performance of Li/GPE/LiCoO2 cell was evaluated and it exhibited a high capacity of 138.01 mAhg?1 with 97% coulombic efficiency for the initial cycle. The cell was stable and retained its high performance with little loss in capacity even after repeated charge–discharge cycles. Such a combination of high ionic conductivity, tensile strength with low thermal shrinkage is seen to be very rare in polymer-based separators. It is noteworthy that this novel GPE outperformed the commercial separator also in the cycle performance. POLYM. COMPOS., 40:2320–2334, 2019. © 2018 Society of Plastics Engineers. © 2018 Society of Plastics Engineers
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    An electroactive ?-phase polyvinylidene fluoride as gel polymer electrolyte for magnesium–ion battery application
    (Elsevier B.V., 2019) Singh, R.; Janakiraman, S.; Khalifa, M.; Anandhan, S.; Ghosh, S.; Adyam, A.; Biswas, K.
    The gel polymer electrolytes (GPEs) are currently interesting research area in rechargeable batteries. In the present study, synthesis and characterization of electroactive gel polymer electrolyte (EGPE) for Mg-ion batteries application have been investigated. The bead free electroactive polyvinylidene fluoride (PVDF) with high porosity is achieved by an electrospinning process. The ?-phase of PVDF is polar and electroactive with a high dipole moment. Electroactive ?-phase is confirmed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). Field emission scanning electron microscopy (FESEM) study is done to analyze the structure and morphology of the electroactive membrane. The electroactive gel polymer electrolyte is formed by immersing an electroactive PVDF membrane in 0.3 M magnesium perchlorate (MgClO4) and propylene carbonate (PC) solution. The ionic conductivity of electroactive ?-phase PVDF membrane is achieved to be 1.49 mS cm?1 at 30 °C, which is higher than commercial available polypropylene (PP) Celgard. Tortuosity of electroactive gel polymer electrolyte is found to be 1.44. The voltage stability of the EGPE is stable up to a high voltage of 5.0 V against Mg+2/Mg. The total ionic transference number and magnesium ion transference number of EGPE are also investigated to confirm high ionic conductivity. © 2019 Elsevier B.V.
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    Origin of ferromagnetism in Cu-doped ZnO
    (Nature Publishing Group Houndmills Basingstoke, Hampshire RG21 6XS, 2019) Ali, N.; Singh, B.; Khan, Z.A.; Vijaya, A.R.; Tarafder, K.; Ghosh, S.
    It is widely reported during last decade on the observation of room temperature ferromagnetism (RTFM) in doped ZnO and other transition metal oxides. However, the origin of RTFM is not understood and highly debated. While investigating the origin of RTFM, magnetic ion doped oxides should be excluded because it is not yet settled whether RTFM is intrinsic or due to the magnetic ion cluster in ZnO. Hence, it is desirable to investigate the origin of RTFM in non-magnetic ion doped ZnO and Cu-doped ZnO will be most suitable for this purpose. The important features of ferromagnetism observed in doped ZnO are (i) observation of RTFM at a doping concentration much below than the percolation threshold of wurtzite ZnO, (ii) temperature independence of magnetization and (iii) almost anhysteretic magnetization curve. We show that all these features of ferromagnetism in ZnO are due to overlapping of bound magnetic polarons (BMPs) which are created by exchange interaction between the spin of Cu 2+ ion and spin of the localized hole due to zinc vacancy (V Z n ). Both the experimental and theoretical investigation show that the exchange interaction between Cu 2+ -Cu 2+ ions mediated by V Z n is responsible for RTFM in Cu-doped ZnO. © 2019, The Author(s).
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    Ferromagnetism from non-magnetic ions: Ag-doped ZnO
    (Nature Research, 2019) Ali, N.; A R, V.; Khan, Z.A.; Tarafder, K.; Kumar, A.; Wadhwa, M.K.; Singh, B.; Ghosh, S.
    To develop suitable ferromagnetic oxides with Curie temperature (TC) at or above room temperature for spintronic applications, a great deal of research in doping ZnO with magnetic ions is being carried out over last decade. As the experimental results on magnetic ions doped ZnO are highly confused and controversial, we have investigated ferromagnetism in non-magnetic ion, Ag, doped ZnO. When Ag replaces Zn in ZnO, it adopts 4d9 configuration for Ag2+ which has single unpaired spin and suitable exchange interaction among these spins gives rise to ferromagnetism in ZnO with above room temperature TC. Experimentally, we have observed room temperature ferromagnetism (RTFM) in Ag-doped ZnO with Ag concentration varied from 0.03% to 10.0%. It is shown that zinc vacancy (VZn) enhances the ferromagnetic ordering (FMO) while oxygen vacancy (VO) retards the ferromagnetism in Ag-doped ZnO. Furthermore, the theoretical investigation revealed that VZn along with Ag2+ ions play a pivotal role for RTFM in Ag-doped ZnO. The Ag2+-Ag2+ interaction is ferromagnetic in the same Zn plane whereas anti-ferromagnetic in different Zn planes. The presence of VZn changes the anti-ferromagnetic to ferromagnetic state with a magnetic coupling energy of 37 meV. Finally, it has been established that the overlapping of bound magnetic polarons is responsible for RTFM in low doping concentration. However, anti-ferromagnetic coupling sets in at higher doping concentrations and hence weakens the FMO to a large extent. © 2019, The Author(s).
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    A high thermally stable polyacrylonitrile (PAN)-based gel polymer electrolyte for rechargeable Mg-ion battery
    (Springer, 2020) Singh, R.; Janakiraman, S.; Khalifa, M.; Anandhan, S.; Ghosh, S.; Adyam, A.; Biswas, K.
    The ionic conductivity and thermal stability of the electrolyte-separator system is an essential parameter for improving battery performance and safety. The present work addresses the high thermally stable gel polymer electrolyte (GPE) using polyacrylonitrile (PAN) as a polymer membrane and magnesium perchlorate in propylene carbonate (Mg(ClO4)2-PC) as a liquid electrolyte. The PAN based polymer membrane is prepared by electrospinning process which produces a bead free and uniformly distributed nanofibers. The electrospun PAN based GPE is characterized by different physical and electrochemical techniques like X-ray diffraction, field emission scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, ionic conductivity, linear sweep voltammetry, magnesium ion transference number and electrochemical impedance spectroscopy. The ionic conductivity of PAN is 3.28 mS cm?1, compared to that of PP Celgard is 1.97 × 10–4 mS cm?1 at 30 °C. The electrochemical stability of PAN is 4.6 V and also exhibits excellent interfacial stability with magnesium metal. The results showed that the PAN-based GPE has higher ionic conductivity and thermal stability than the polypropylene (PP) Celgard membrane. © 2020, Springer Science+Business Media, LLC, part of Springer Nature.