School Of Basic And Applied Sciences
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Item A glimpse on all-solid-state Li-ion battery (ASSLIB) performance based on novel solid polymer electrolytes: a topical review(Springer, 2020) Arya, A; Sharma, A.L.All-solid-state batteries are swiftly gaining the attention of the research community owing to their widespread applications in electric vehicles, digital electronics, portable appliances, etc. A battery comprises three components: cathode, anode and electrolyte. An electrolyte is the heart of the battery and plays a crucial role in the overall performance of the battery. In order to make the review more focused, all-solid-state Li-ion batteries (ASSLIBs) have been considered. This review covers the architecture of ASSLIBs, advantages, and characteristics of the solid polymer electrolytes. The important preparation methods are summarized, followed by the characterizations for testing the suitability of electrolytes for solid-state batteries. The discussion is focused on the "state of the art" in the field of solid-state batteries, device fabrication, and comparison in terms of capacity, energy density, and cyclic stability. In the last section, the ion conduction mechanism in different solid polymer electrolytes is discussed. Finally, it is tried to give a possible outlook for developing future hybrid and multifunctional electrolytes which can act as a bridge for developing solid-state batteries covering a broad range of applications. - 2020, Springer Science+Business Media, LLC, part of Springer Nature.Item Ion transport, dielectric, and electrochemical properties of sodium ion-conducting polymer nanocomposite: application in EDLC(Springer, 2020) Kumar, A; Madaan, M; Arya, A; Tanwar, S; Sharma, A.L.The present paper reports the investigation of structural, electrical, dielectric, and transport properties of the polyethylene oxide (PEO)-based polymer nanocomposite (PNC), with sodium hexafluorophosphate (NaPF6) salt and barium titanate (BaTiO3) as nanofillers. The PNC has been prepared via standard solution casting technique. The structural investigation has been investigated by X-ray diffraction and evidence the enhancement in amorphous content. The morphology has been examined by Field emission scanning electron microscopy technique and confirms the composite formation. The presence of polymer-ion and ion-ion interaction has been confirmed by the Fourier transform infrared spectra (FTIR) and evidences the PNC formation. The impedance spectroscopy has been performed to evaluate the ionic conductivity in the temperature range 40–100 °C.The increase of conductivity is obtained with the addition of nanofiller and temperature-dependent conductivity follows Arrhenius behavior. The PNC film having the highest conductivity exhibits low activation energy and indicates the fast ion migration. The ion transference number is close to unity and the voltage stability window is within the desirable limit. The complex permittivity and complex conductivity have been obtained and the plot has been fitted in the whole frequency window. The fitted plot is in perfect agreement with experimental data. The PNC having the highest conductivity has high dielectric strength and low relaxation time. It confirms the nanofiller role in enhancing ion migration. The ion transport parameters (n, ?, D) are also in correlation with impedance and dielectric analysis. The optimized PNC films have been used to prepare the Electric double-layer capacitors (EDLC) and it demonstrates the improved performance which may be attributed to the effective role played by nanofiller in boosting ion dynamics. - 2020, Springer Science+Business Media, LLC, part of Springer Nature.Item Investigation on enhancement of electrical, dielectric and ion transport properties of nanoclay-based blend polymer nanocomposites(Springer, 2019) Arya, A; Sharma, A.L.An intercalated blend polymer nanocomposite (PNC) films based on blend (PEO–PVC), LiPF6 as salt and modified montmorillonite (MMMT) as nanoclay are prepared via solution cast method. The impact of the nanoclay on the morphology, structure, polymer–polymer, polymer–ion interactions, ionic conductivity, voltage stability window, glass transition temperature, dielectric permittivity, and ac conductivity has been explored. The structural analysis evidenced the formation of blended and intercalated polymer nanocomposites. The FTIR analysis confirmed the interaction between polymer–ion-nanoclay, and polymer intercalation is evidenced by the out-of-the-plane mode [Si–O mode] of MMMT. An increase in the fraction of free anions with clay addition is confirmed. The highest ionic conductivity of about ~ 8.2 × 10−5 S cm−1 (at RT) and 1.01 × 10−3 S cm−1 (at 100 °C) is exhibited by 5 wt% MMMT based PNC. A strong correlation is observed between the glass transition temperature, crystallinity, melting temperature (Tm), ionic conductivity, relaxation time, and dielectric strength. The dielectric data have been fitted and enhanced dielectric strength and lowering of the relaxation time (τε′andτm) with clay addition evidences the faster segmental motion of polymer chain. The intercalated PNC shows thermal stability up to ~ 300 °C, high ion transference number (~ 1), and broad voltage stability window of ~ 5 V. An absolute agreement between ion mobility (μ), diffusion coefficient (D), and ionic conductivity is observed. An ion transport mechanism has been proposed on the basis of experimental results. Therefore, the proposed PNC can be adopted as electrolyte cum separator for energy storage devices. © 2019, Springer-Verlag GmbH Germany, part of Springer Nature.Item Tailoring of the structural, morphological, electrochemical, and dielectric properties of solid polymer electrolyte(Institute for Ionics, 2019) Arya, A; Sharma, A.L.A solid polymer electrolyte composed of poly(ethylene oxide) and sodium hexafluorophosphate has been synthesized with a varying fraction of succinonitrile via solution cast technique. Impedance spectroscopy, transference number measurements, and linear sweep voltammetry were used to study the electrochemical properties. The 10 wt.% succinonitrile system exhibited the highest ionic conductivity of ~ 2 × 10−5 S cm−1 which is two orders of magnitude higher than the pristine polymer salt system. The high ionic transference number (~ 1) confirms that ion conduction is dominated by ions and displays the voltage stability window of about 4 V. The dielectric permittivity and the relaxation time (τε′,τM,τh) values corresponding to the segmental motion of the polymer chain varies with the variation of succinonitrile content. The relaxation time and double-layer capacitance are in good agreement with the conductivity. Finally, an ion transport mechanism has been proposed to provide a better understanding of ion migration. © 2019, Springer-Verlag GmbH Germany, part of Springer Nature.Item Dielectric relaxation and AC conductivity of TiO2 nanofiller dispersed polymer nanocomposite(American Institute of Physics, 2019) Arya, A; Sadiq, M; Sharma, A.L.The Lithium-ion conducting polymer nanocomposite (PNC) has been synthesized by the standard solution cast technique in the skeleton of PEO-PVC blend with a different content of Titanium oxide (TiO2) as nanofiller. The lithium hexafluorophosphate (LiPF6) was used as the salt. The dielectric strength decreases with frequency and is attributed to the dominance of the electrode polarization effect. The highest dielectric strength and lowest relaxation time (1.88ns) were achieved for the 15 wt. % TiO2 (PPS15T) PNCs when compared to other concentrations. The PPS15T exhibits the highest dc conductivity 2.34×10-5 S cm-1 at RT. The dielectric strength (Δϵ) and relaxation time (τϵ′) were in good agreement with the dc conductivity (σdc). An interaction scheme has also been proposed to highlight the interactions between the polymer, salt and nanofiller in most visual manner. © 2019 Author(s).Item Effect of variation of different nanofillers on structural, electrical, dielectric, and transport properties of blend polymer nanocomposites(Institute for Ionics, 2018) Arya,Anil; Sadiq, Mohd; Sharma, A.L.In the present work, the effect of various nanofillers with different particle sizes and dielectric constants (BaTiO3, CeO2, Er2O3, or TiO2) on blend solid polymer electrolyte comprising PEO and PVC complexed with bulky LiPF6 has been explored. The XRD analysis confirms the polymer nanocomposite formation. FTIR provides evidence of interaction among the functional groups of the polymer with the ions and the nanofiller in terms of shifting and change of the peak profile. The highest ionic conductivity is ~ 2.3 x10−55 S cm−1 with a wide electrochemical stability window of f ~ 3.5 V for 10 wt% Er2O3. The real and imaginary parts of dielectric permittivity follow the identical trend of the decreasing value of dielectric permittivity and dielectric loss with increase in the frequency. The particle size and the dielectric constant show an abnormal trend with different nanofillers. The AC conductivity follows the universal Jonscher power law, and an effective mechanism has been proposed to understand the nanofiller interaction with cation coordinated polymer.Item Structural, electrical properties and dielectric relaxations in Na+-ion-conducting solid polymer electrolyte(Institute of Physics Publishing, 2018) Arya, A.; Sharma, A.L.In this paper, we have studied the structural, microstructural, electrical, dielectric properties and ion dynamics of a sodium-ion-conducting solid polymer electrolyte film comprising PEO8-NaPF6+ x wt. % succinonitrile. The structural and surface morphology properties have been investigated, respectively using x-ray diffraction and field emission scanning electron microscopy. The complex formation was examined using Fourier transform infrared spectroscopy, and the fraction of free anions/ion pairs obtained via deconvolution. The complex dielectric permittivity and loss tangent has been analyzed across the whole frequency window, and enables us to estimate the DC conductivity, dielectric strength, double layer capacitance and relaxation time. The presence of relaxing dipoles was determined by the addition of succinonitrile (wt./wt.) and the peak shift towards high frequency indicates the decrease of relaxation time. Further, relations among various relaxation times () have been elucidated. The complex conductivity has been examined across the whole frequency window; it obeys the Universal Power Law, and displays strong dependency on succinonitrile content. The sigma representation () was introduced in order to explore the ion dynamics by highlighting the dispersion region in the Cole-Cole plot () in the lower frequency window; increase in the semicircle radius indicates a decrease of relaxation time. This observation is accompanied by enhancement in ionic conductivity and faster ion transport. A convincing, logical scheme to justify the experimental data has been proposed. ? 2018 IOP Publishing Ltd.Item Structural, microstructural and electrochemical properties of dispersed-type polymer nanocomposite films(Institute of Physics Publishing, 2018) Arya, A.; Sharma, A.L.Free-standing solid polymer nanocomposite (PEO-PVC) + LiPF6-TiO2 films have been prepared through a standard solution-cast technique. The improvement in structural, microstructural and electrochemical properties has been observed on the dispersion of nanofiller in polymer salt complex. X-ray diffraction studies clearly reflect the formation of complex formation, as no corresponding salt peak appeared in the diffractograms. The Fourier transform infrared analysis suggested clear and convincing evidence of polymer-ion, ion-ion and polymer-ion-nanofiller interaction. The highest ionic conductivity of the prepared solid polymer electrolyte (SPE) films is ?5 10-5 S cm-1 for 7 wt.% TiO2. The linear sweep voltammetry provides the electrochemical stability window of the prepared SPE films, about ?3.5 V. The ion transference number has been estimated, t ion = 0.99 through the DC polarization technique. Dielectric spectroscopic studies were performed to understand the ion transport process in polymer electrolytes. All solid polymer electrolytes possess good thermal stability up to 300 ?C. Differential scanning calorimetry analysis confirms the decrease of the melting temperature and signal of glass transition temperature with the addition of nanofiller, which indicates the decrease of crystallinity of the polymer matrix. An absolute correlation between diffusion coefficient (D), ion mobility (?), number density (n), double-layer capacitance (C dl), glass transition temperature, melting temperature (T m), free ion area (%) and conductivity (?) has been observed. A convincing model to study the role of nanofiller in a polymer salt complex has been proposed, which supports the experimental findings. The prepared polymer electrolyte system with significant ionic conductivity, high ionic transference number, and good thermal and voltage stability could be suggested as a potential candidate as electrolyte cum separator for the fabrication of a rechargeable lithium-ion battery system. ? 2018 IOP Publishing Ltd.Item Optimization of salt concentration and explanation of two peak percolation in blend solid polymer nanocomposite films(Springer New York LLC, 2018) Arya, A.; Sharma, A.L.The present paper is focused toward the preparation of the flexible and free-standing blend solid polymer electrolyte films based on PEO-PVP complexed with NaPF6 by the solution cast technique. The structural/morphological features of the synthesized polymer nanocomposite films have been investigated in detail using X-ray diffraction, Fourier transform infra-red spectroscopy, Field emission scanning electron microscope, and Atomic force microscopy techniques. The film PEO-PVP + NaPF6 ((Formula presented.)8) exhibits highest ionic conductivity ~ 5.92 ? 10?6 S cm?1 at 40 ?C and ~ 2.46 ? 10?4 S cm?1 at 100 ?C. The temperature-dependent conductivity shows an Arrhenius type behavior and activation energy decreases with the addition of salt. The high temperature (100 ?C) conductivity monitoring is done for the optimized PEO-PVP + NaPF6 ((Formula presented.)8) highly conductive system and the conductivity is still maintained stable up to 160 h (approx. 7 days). The thermal transitions parameters were measured by the differential scanning calorimetry (DSC) measurements. The prepared polymer electrolyte film displays the smoother surface on addition of salt and a thermal stability up to 300 ?C. The ion transference number (tion) for the highest conducting sample is found to be 0.997 and evidence that the present system is ion dominating with negligible electron contribution. Both linear sweep voltammetry and cyclic voltammetry supports the use of prepared polymer electrolyte with long-term cycle stability and thermal stability for the solid-state sodium ion batteries. Finally, a two peak percolation mechanism has been proposed on the basis of experimental findings. [Figure not available: see fulltext.] ? 2018 Springer-Verlag GmbH Germany, part of Springer NatureItem Insights into the use of polyethylene oxide in energy storage/conversion devices: A critical review(Institute of Physics Publishing, 2017) Arya, A.; Sharma, A.L.In this review, the latest updates in poly (ethylene oxide) based electrolytes are summarized. The ultimate goal of researchers globally is towards the development of free-standing solid polymeric separators for energy storage devices. This single free-standing solid polymeric separator may replace the liquid and separator (organic/inorganic) used in existing efficient/smart energy technology. As an example, polyethylene oxide (PEO) consists of an electron donor-rich group which provides coordinating sites to the cation for migration. Owing to this exclusive structure, PEO exhibits some remarkable properties, such as a low glass transition temperature, excellent flexibility, and the ability to make complexation with various metal salts which are unattainable by another polymer host. Hence, the PEO is an emerging candidate that has been most examined or is currently under consideration for application in energy storage devices. This review article first provides a detailed study of the PEO properties, characteristics of the constituents of the polymer electrolyte, and suitable approaches for the modification of polymer electrolytes. Then, the synthesization and characterizations techniques are outlined. The structures, characteristics, and performance during charge-discharge of four types of electrolyte/separators (liquid, plasticized, and dispersed and intercalated electrolyte) are highlighted. The suitable ion transport mechanism proposed by researchers in different renowned groups have been discussed for the better understanding of the ion dynamics in such systems. ? 2017 IOP Publishing Ltd.